CN1735576A - 使用换热器制备直链α－烯烃低聚物的方法 - Google Patents

使用换热器制备直链α－烯烃低聚物的方法 Download PDF

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CN1735576A
CN1735576A CNA038229943A CN03822994A CN1735576A CN 1735576 A CN1735576 A CN 1735576A CN A038229943 A CNA038229943 A CN A038229943A CN 03822994 A CN03822994 A CN 03822994A CN 1735576 A CN1735576 A CN 1735576A
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P·阿诺迪
E·J·M·德波尔
R·莫伊尼
A·范宗
P·E·昂格
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Abstract

本发明涉及一种在含有液相和气相的反应器中制备直链α－烯烃低聚物的方法，该方法包括在放热条件下于2，6－二(芳亚氨基)吡啶衍生物的铁络合物存在下催化低聚乙烯成为平均分子量为50－350的α－烯烃低聚物、和采用不与液相直接接触的换热器使用至少部分气相作为冷却介质移走热量的步骤。本发明还涉及用于实施所述方法的装置。

Description

使用换热器制备直链α-烯烃低聚物的方法
本发明涉及在含有液相和气相的反应器中制备直链α-烯烃低聚物的方法，其包括在放热条件下于2，6-二(芳亚氨基)吡啶衍生物的铁络合物存在下催化低聚乙烯成为平均分子量为50-350的α-烯烃低聚物、和采用换热器移走热量的步骤。
已知有多种方法用于制备高级直链α-烯烃(例如，D.Vogt，Oligomerisation of ethylene to higher a-olefins in AppliedHomogeneous Catalysis with Organometallic Compounds，Ed.B.Cornils，W.A.Herrmann，2nd Edition，Vol.1，Ch.2.3.1.3，page240-253，Wiley-VCH 2002)。这些工业化方法能够获得泊松(Poisson)或舒尔茨-弗洛里(Schulz-Flory)低聚物产物分布。在这类方法中，通常制得多种低聚物。在WO02/00339、WO02/12151、WO02/06192、WO02/28805、WO01/58874和WO99/02472中，公开了新型Fe基乙烯低聚催化剂，该催化剂对直链α-烯烃具有高的活性和高的选择性。这些催化剂(引入它们以供参考)是基于一种选择的2，6-吡啶二羧基醛二亚胺或一种选择的2，6-二酰基吡啶二亚胺的铁络合物。
在本发明中，术语“二-(芳亚氨基)-吡啶”用来描述两类配体。α-烯烃低聚物是通式为H2C＝CH-(CH2CH2)nH的化合物或这类化合物的混合物，其中n是1或更大的整数。在这类低聚物中，α-烯烃低聚物通常是平均数n为1-20、优选为2-10的α-烯烃低聚物的混合物。由本发明方法制得的α-烯烃低聚物的平均分子量优选在50-350之间，更优选在60-280之间，甚至更优选在80-210之间。
在上述铁络合物存在下的乙烯反应通常是在充分混合的反应器中使用质子惰性有机溶剂于液相中进行的。此反应产生大量的热量，该热量应该被移走。如WO02/06192所述，优选是将多个小反应器和多个换热器组合安装，以为该反应器系统提供充足的冷却能力。工艺温度(通常在约35-90℃之间，更优选在约35-75℃之间)在多个方面影响着该α-烯烃的生产成本。该温度越高，则必须应用于反应器的换热器就越小，这通常会降低成本。活性低聚催化剂的劣化随着温度升高而加速。已经发现，与良好的绝对催化剂生产能力耦合的最大体积的α-烯烃产量通常发生在约45-75℃的温度范围内，所以这个温度范围是优选的。最后，该温度还会影响泡点压力、液相中的乙烯量和催化剂选择性。该温度越高，则保持催化剂选择性所需要的压力也越高，这将提高生产厂家的投资成本，这是因为例如需要更厚的容器和更大的压缩机以获得更高的乙烯压力。较高压力还会提高能量成本。
用于该反应中的乙烯低聚催化剂的量优选为该反应器的冷却能力和从气相到液相的乙烯质量传递所能允许的最大值。催化剂可以仅添加到第一反应器中或添加到一个或多个串联的连续反应器中。每个反应器中可添加不同量的催化剂。低聚反应是极为放热的，约100kJ/mol被低聚的乙烯，因而，为了保持所希望的工艺温度同时保持高的反应器体积生产能力，通常要对反应器进行冷却。
在现有技术中，冷却是通过使冷却管穿过一个或多个反应器内部的液体以冷却其内容物而实现的。另一种冷却方法是在该反应器外部配置一个或多个换热器，并通过液体回路与反应器相连以冷却反应器的内容物。这些外部换热器可以为典型的管壳式换热器。所述反应器也可包上冷却夹套。可以冷却进料到部分或全部反应器中的部分或全部原料，以使这些成分的显热冷却反应器。但所有这些液体冷却方法，都存在着冷却器的蜡和聚乙烯结垢的缺点，这必须定期关闭反应器，以清洁冷却器。而且，蜡和聚乙烯结垢可能会提高溶剂的链烷烃含量。
因此，本发明一个目的是设计一种没有上述缺点的方法。现在已经发现，直链α-烯烃低聚物可在包含液相和气相的反应器中制得，其中包括在放热条件下于2，6-二(芳亚氨基)吡啶衍生物的铁络合物存在下催化低聚乙烯成为平均分子量为50-350的α-烯烃低聚物、和采用不与液相直接接触的换热器使用至少部分气相作为冷却介质移走热量的步骤。
这种方法提供了一种冷却系统，其冷却元件位于液相反应介质外部。由于蜡和聚乙烯具有高的沸点，所以蜡和聚乙烯的沉积不再发生，且换热器的结垢可有效抑制。
本发明的换热器是常规类型的，如管壳式换热器等。换热器采用常规冷却流体如水、氨、Freon等进行内部冷却。反应热使得反应介质内的溶剂、反应物和/或反应产物蒸发并随后被换热器所冷却，之后再用作反应器的冷却介质。换热器可设置在反应器内部或外部。当换热器设置在反应器内部时，优选在热器表面上发生一些冷凝。当换热器设置在反应器外部时，优选使反应器冷却介质从反应器的气相经过换热器、压缩机/泵和任选的气液分离器强制循环回到反应器的液相。这将会附加改善反应器内的混合。在冷却此回路中的反应器冷却介质之后，会发生一些冷凝。这将允许使用气-液分离器应用分离的气体和液体返回到反应器。而且，可以故意从此气-液分离器移走(部分)液相并将它直接送到产物处理区。最后，如果发生全部冷凝，则可通过泵替代压缩机将这种液体返回到反应器，这能降低成本。这种反应器冷却介质选自烷烃、烯烃、芳族化合物及其混合物，优选为丙烷、正戊烷、异戊烷、乙烯、1-丁烯、邻-、间-和对-二甲苯、甲苯及其混合物。
本发明方法的其它优点是可以仅用一个反应器，因为其效率和不结垢而不需要使用多个小反应器。这明显进一步降低了低聚反应的成本。
可用于上述方法中的2，6-二(芳亚氨基)吡啶型铁络合物是本领域已知的，在WO02/00339、WO02/12151、WO02/06192、WO02/28805、WO01/58874和WO99/02472中有述。任意的这些络合物都可使用。但最好结果可由特定铁络合物获得，即其中2，6-二(芳亚氨基)吡啶衍生物的一个芳基部分是被基团CH2R或C2H5R 2，6-二取代的，其中R选自H、F和取代或未取代的芳基，优选选自H和F，另一个芳基部分是2，6-未取代的，或其中2，6-二(芳亚氨基)吡啶衍生物的两个芳基部分都是被F或Cl 2，6-二取代的。
特别有用的是具有下述通式的2，6-二(芳亚氨基)吡啶衍生物：
Figure A0382299400071
其中
R1是H或CH3；
R2是H、叔丁基或苯基；和
R3是H、叔丁基或OR′，其中R′表示CH3、Si(CH3)3或二十烷基(C20H41)；和
Figure A0382299400072
术语“芳基”表示芳族基团，如苯基、萘基、噻吩基、吡啶基、吡咯基等。苯基是优选的芳基。优选的苯基是被CH3、叔丁基、F或OR′取代的，其中R′表示CH3或Si(CH3)3。
在一个优选实施方式中，铝基助催化剂可添加到液相中，优选是甲基铝氧烷。当助催化剂如烷基铝化合物对于该活性催化剂物质来说需要或优选时，2，6-二(芳亚氨基)吡啶衍生物的铁络合物，如2，6-二(芳亚氨基)吡啶衍生物与FeCl2的络合物，可与烷基铝化合物、优选为铝氧烷进行反应，形成一种活性乙烯低聚物质。具体的烷基铝化合物包括甲基铝氧烷(一种具有通式(MeAlO)n的低聚物)、(C2H5)2AlCl、C2H5AlCl2、(C2H5)3Al和((CH3)2CHCH2)3Al。特别优选的铝氧烷是甲基铝氧烷。在低聚反应中，铝(作为烷基铝化合物)与铁(作为络合物)的比值可以为约10-10000。
本发明催化剂体系的另一种优选成分是第二助催化剂化合物，选自ZnR′2，其中每个R′(其可以相同或不同)选自氢、任选取代的C1-C20烃基、苯基、Cl、Br、I、SR″、NR″2、OH、OR″、CN、NC，其中R″(其在同一分子中可以相同或不同)是C1-C20烃基。
在本发明的优选催化剂体系中，第二助催化剂化合物是ZnR′2，其中R′是C1-C20烃基，更优选为C1-C20烷基，甚至更优选为C1-C6烷基。合适的烷基包括甲基、乙基、丙基、丁基等。特别优选地，R′基团是C1-C3烷基，尤其是乙基。
该第二助催化剂与该铝基助催化剂一起组合使用，对于提高乙烯低聚反应中直链α-烯烃选择性、和降低不想要的副产物如支链烯烃、内烯烃、2，2-二取代烯烃和二烯烃的量来说是特别有用的。
要说明的是，当铝基助催化剂的金属与第二助催化剂的金属的摩尔比为5∶1-1∶5之间、优选在3∶1-1∶3之间、更优选在2∶1-1∶2之间、尤其是1∶1时，可以获得特别高的直链α-烯烃的选择性。
还可向本发明的催化剂体系中添加其它任选成分，例如路易斯酸和碱，例如在WO02/28805中公开的那些。
该活性催化剂体系可通过将2，6-二(芳亚氨基)吡啶衍生物的铁络合物或乙酰丙酮合铁络合物与合适的2，6-二(芳亚氨基)衍生物(配体)的混合物、第一助催化剂化合物、第二助催化剂化合物和任意任选的其它成分混合在一起而制成，优选在溶剂中进行混合。
在这种生产工厂的投资成本中及其操作成本中的重要一项是该工艺中必须要循环的反应器冷却介质的量。气态反应器冷却介质的循环通常涉及进行再压缩以对一个或多个反应器进料。压缩机和相关设备大大增加了投资和操作成本。在本发明方法中，优选选择冷却介质以完全溶解乙烯。在这种情形中，冷却介质仅需要单个反应器和冷凝器，而一个简单的循环泵就足够了。这样，如使用昂贵循环鼓风机的昂贵循环就不再需要了，这进一步增加了本发明方法的优点。
本发明可由下述表示可用来实施本发明方法的装置示意图的附图进行描述，但这些附图无论如何不用来限制本发明。
图1是用于实施本发明方法的带有设置在反应器外部的换热器的装置示意图。
图2是用于实施本发明方法的带有设置在反应器内部的换热器的装置示意图。
图1给出包括液相3和气相4的反应器2，两相之间通过气/液界面12处于平衡状态。液相包括乙烯、2，6-二(芳亚氨基)吡啶衍生物的铁络合物、α-烯烃低聚物、任选的溶剂和如助催化剂之类的辅剂。选择任选溶剂来溶解乙烯。反应器包括入口10(反应器原料1由此被输入)、气体出口11和反应器底部出口9。在图1所示实施方式中，出口11通过管线14与换热器5a相连，而换热器5a通过管线15与气-液分离器6相连。如果需要，管线15可包含压缩机7a。气-液分离器6具有用于输送液体的出口17，任选通过泵8输送，以获得压缩的液体物流17，该物流经由管线19循环回到反应器2。气体通过管线16离开气-液分离器6，管线16任选包含压缩机7b和/或换热器5b，以获得冷却气体物流18，该物流循环回到反应器2中。如果在管线15中没有发生冷凝，则气-液分离器6和泵8是多余的，可以省去。在此情形下，管线15可直接与压缩机7b和/或换热器5b(如果有的话)相连，或与管线19相连。反应器2可包括任选的雾沫分离器13。
图2给出了本发明另一种实施方式。在这种实施方式中，反应器原料1通过入口10引入到反应器2中。反应器中的液相3通过气/液界面12与气相4处于平衡状态。在含有气相6的反应器部分，设置有不与液相3接触的换热器20。气相6部分可任选包括雾沫分离器13。换热器20冷却气体，之后至少部分气体发生冷凝，冷却的冷凝物从换热器20的表面落到液相3中，从而冷却流体介质。反应产物接着通过反应器底部出口9排出反应器。
因此，根据本发明的又一个方面，提供了一种用于实施上述制备直链α-烯烃低聚物的方法的装置，该装置包括可容纳液相(3)和气相(4)的反应器(2)、可由其输入反应器原料(1)的入口(10)、反应器底部出口(9)、设置以防止与液相(3)直接接触的至少一个换热器(5a，b；20)、以及进一步任选的气体出口(11)、泵(8)、压缩机(7a，b)、雾沫分离器(13)和/或气/液分离器(6)。

Claims (8)

1.一种用于在含有液相和气相的反应器中制备直链α-烯烃低聚物的方法，该方法包括在放热条件下于2，6-二(芳亚氨基)吡啶衍生物的铁络合物存在下催化低聚乙烯成为平均分子量为50-350的α-烯烃低聚物、和采用不与液相直接接触的换热器使用至少部分气相作为冷却介质移走热量的步骤。
2.权利要求1的方法，其中向液相中添加铝基助催化剂，优选是甲基铝氧烷。
3.权利要求1或2的方法，其中所述平均分子量在60-280之间，更优选在80-210之间。
4.权利要求1-3任一项的方法，其中所述2，6-二(芳亚氨基)吡啶衍生物的一个芳基部分是被基团CH2R或C2H5R 2，6-二取代的，其中R选自H和F，另一个芳基部分是2，6-未取代的，或其中所述2，6-二(芳亚氨基)吡啶衍生物的两个芳基部分都是被F或Cl 2，6-二取代的。
5.权利要求1-4任一项的方法，其中所述2，6-二(芳亚氨基)吡啶衍生物具有下述通式：
Figure A038229940002C1
其中
R1是H或CH3；
R2是H、叔丁基或苯基；和
R3是H、叔丁基或OR′，其中R′表示CH3、Si(CH3)3或二十烷基(C20H41)；或
Figure A038229940003C1
6.权利要求1-5任一项的方法，其中所述冷却介质选自烷烃、烯烃、芳族化合物及其混合物。
7.权利要求1-6任一项的方法，其中所述冷却介质选丙烷、正戊烷、异戊烷、乙烯、1-丁烯、邻-、间-和对-二甲苯、甲苯及其混合物。
8.一种用于实施权利要求1-7任一项的制备直链α-烯烃低聚物的方法的装置，该装置包括可容纳液相(3)和气相(4)的反应器(2)、可由其输入反应器原料(1)的入口(10)、反应器底部出口(9)、设置以防止与液相(3)直接接触的至少一个换热器(5a，b；20)、以及进一步任选的气体出口(11)、泵(8)、压缩机(7a，b)、雾沫分离器(13)和/或气/液分离器(6)。
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