CN101495429A - 用于乙烯和/或α-烯烃的寡聚化/多聚化的方法和设备 - Google Patents

用于乙烯和/或α-烯烃的寡聚化/多聚化的方法和设备 Download PDF

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CN101495429A
CN101495429A CNA2007800278528A CN200780027852A CN101495429A CN 101495429 A CN101495429 A CN 101495429A CN A2007800278528 A CNA2007800278528 A CN A2007800278528A CN 200780027852 A CN200780027852 A CN 200780027852A CN 101495429 A CN101495429 A CN 101495429A
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P·弗里茨
H·博尔特
A·基辛格
W·穆勒
F·温克勒
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Saudi Basic Industries Corp
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Abstract

本发明涉及一种用于乙烯和/或α－烯烃的寡聚化/多聚化的方法，包括如下步骤：对乙烯和/或α－烯烃进行寡聚化/多聚化；将所得的产物分离为至少一种可商品化的产物以及一种或多种不可商品化的级分；并将所述一种或多种不可商品化的级分送入蒸汽裂化炉中进行蒸汽裂化。

Description

用于乙烯和/或α-烯烃的寡聚化/多聚化的方法和设备
本发明涉及一种用于乙烯和/或α-烯烃的寡聚化/多聚化的方法和设备。
使用有机金属催化剂--适当地在有机溶剂中--进行的乙烯和/或α-烯烃的寡聚化/多聚化在本领域中是公知的。特别是对于乙烯的寡聚化，会得到相当宽泛的产物谱，其中既有所需要的C4-C20线性α-烯烃(LAO)，也有含有多于20个碳原子的高级线性α-烯烃，甚至还有多聚化产物。因此，在寡聚化/多聚化之后必须将产物分离为可商品化的产物和含有不合格(offspec)产物的不可商品化的级分。不可商品化的级分可能含有不符合产品说明书规定的或者保证的的产物或产物级分(即不合格产品)，或者含有因为经济原因不可商品化的产物。经济原因可能包括没有足够的用于加工、处理的基础设施或者例如装载装置。此外，对于某种特殊的产物或级分而言，由于产量很小、运输和后勤成本很高以及在某地区的市场价格较低，其商品化是不经济的。
在现有技术中，这种不可商品化的或者不合格的级分或产物通常都被焚化，因为焚化被认为是处理不可商品化的产物的最经济的途径。
然而，焚化和产生的二氧化碳对于环境平衡有着非常大的负面影响。
因此，本发明的一个目的是提供一种能够克服现有技术中的缺陷的用于乙烯和/或α-烯烃的寡聚化/多聚化的方法。特别是提供这样一种方法--该方法能够避免焚化不可商品化的级分或产物，且提供一种使它们能被再利用的替代途径。
此外，还将提供一种用于寡聚化/多聚化的的设备。
本发明的第一个目的通过一种用于乙烯和/或α-烯烃的寡聚化/多聚化的方法实现，所述方法包括如下步骤：对乙烯和/或α-烯烃进行寡聚化/多聚化；将所得的产物分离为至少一种可商品化的产物以及一种或多种不可商品化的级分；并将所述一种或多种不可商品化的级分送入蒸汽裂化炉中进行蒸汽裂化。
优选地，乙烯在上述第一步骤中被寡聚化而形成线性α-烯烃。
在一个实施方案中，在分离之前，可将用于寡聚化/多聚化过程的催化剂失活和/或除去，并可除去寡聚化/多聚化过程中使用的溶剂。
通过蒸馏、过滤或类似方法，可以容易地实现可商品化的和不可商品化的寡聚化/多聚化级分或产物的分离。
更优选地，蒸汽裂化产物(优选为乙烯)在经过充分的分离和纯化之后可被再循环用于寡聚化/多聚化步骤中。
本发明的第二个目的通过一种用于乙烯和/或α-烯烃的寡聚化/多聚化的设备实现，所述设备包括一个寡聚化/多聚化反应器和一个与该反应器相连接的蒸汽裂化炉。
优选地，所述蒸汽裂化炉具有一条再循环线，以用于将蒸汽裂化产物在通过相应的分离和纯化装置之后再循环回下游寡聚化/多聚化反应器中。
令人意外地发现，在本发明的方法中，乙烯和/或α-烯烃的寡聚化/多聚化生成的不可商品化的或不合格的级分或产物可被有利地转移至蒸汽裂化炉中，这样可使得这些不可商品化的蒸汽被转化为具有很高乙烯产率的蒸汽裂化产物。还发现，包括本发明设备的石油化工复合设备的总体经济效率具有明显的改善。此外，由于避免了焚化步骤，对于环境平衡也有着积极的效果。
蒸汽裂化在石油化工产业中是公知的。在蒸汽裂化过程中，饱和烃类通常被裂化为较小的、通常不饱和的烃类。这是一种生产较轻烯类(包括乙烯和丙烯)的基本的工业方法。
在蒸汽裂化中，例如石脑油、LPG或乙烷的气态或液态烃类进料被蒸汽稀释，然后在炉中被短暂地加热(很明显，该过程中不存在氧气)。通常，反应温度相当高(约为850℃)，但是反应时间应被控制得很短。在蒸汽裂化反应中产生的产物依赖于下列因素：进料的组成、烃类与蒸汽的比例、裂化温度和在炉内的滞留时间。
到目前为止，在现有技术中还没有关于将常规的寡聚化/多聚化反应器与蒸汽裂化炉相组合的启示。
根据本发明的方法，优选地在存在有机溶剂和均一催化剂的条件下，将例如乙烯和α-烯烃的单体引入一个寡聚化/多聚化反应器中。所述均一催化剂优选地可含有锆组分和有机铝组分。所述锆组分可具有通式ZrCl4-mXm，其中X为OCOR或OSO3R’，R和R’各自独立地为烷基、烯基和苯基，并且其中0＜m＜4。所述有机铝组分优选地可为Al(C2H5)3、Al2Cl3(C2H5)3或AlCl(C2H5)2。在寡聚化/多聚化反应器中得到的产物包括可商品化的和不可商品化(不合格)的级分或产物，它们将会被分离。在寡聚化/多聚化之后，所用的催化剂被失活和除去，任选地溶剂也被除去，所述级分通过例如蒸馏或过滤(如果得到的是固体的高分子量寡聚物的话)的方法而被分离。
然后将所述一种或多种不可商品化的级分送入蒸汽裂化炉中，在炉中这些级分可被转化为常规的蒸汽裂化产物，特别是可获得高产率的乙烯。然后这些乙烯在经过分离和纯化之后可被再循环回寡聚化/多聚化反应器中或者用于其他用途。
本发明方法避免了目前为止一直使用的对不可商品化的级分或产物的焚化过程，并且提高了设备的总体经济效率。
在上述说明书和权利要求书中公开的各个特征都可以分别地或以任一组合地用于以各种形式实现本发明。

Claims (9)

1.用于乙烯和/或α-烯烃的寡聚化/多聚化的方法，包括如下步骤：对乙烯和/或α-烯烃进行寡聚化/多聚化；将所得的产物分离为至少一种可商品化的产物以及一种或多种不可商品化的级分；并将所述一种或多种不可商品化的级分送入蒸汽裂化炉中进行蒸汽裂化。
2.根据权利要求1的方法，其中在第一步骤中，乙烯被寡聚化而形成线性α-烯烃。
3.根据权利要求1或2的方法，其中在分离之前，将用于寡聚化/多聚化过程的催化剂失活和/或除去，并除去寡聚化/多聚化过程中使用的溶剂。
4.根据前述权利要求任一项的方法，其中蒸汽裂化产物，优选为乙烯，在经过充分的分离和纯化之后被再循环用于寡聚化/多聚化步骤中。
5.用于乙烯和/或α-烯烃的寡聚化/多聚化的设备，包括一个寡聚化/多聚化反应器和一个与该反应器相连接的蒸汽裂化炉。
6.根据权利要求5的设备，其中所述蒸汽裂化炉具有一条再循环线，以用于将蒸汽裂化产物在充分的分离和纯化之后再循环回寡聚化/多聚化反应器中。
7.根据权利要求1至4任一项的方法，其中使用一种均一催化剂进行寡聚化，所述均一催化剂包括一种锆组分和一种有机铝组分。
8.根据权利要求7的方法，其中所述锆组分具有通式ZrCl4-mXm，其中X为OCOR或OSO3R’，R和R’各自独立地为烷基、烯基和苯基，并且其中0＜m＜4。
9.根据权利要求7或8的方法，其中所述有机铝组分为Al(C2H5)3、Al2Cl3(C2H5)3或AlCl(C2H5)2。
CNA2007800278528A 2006-07-31 2007-06-05 用于乙烯和/或α-烯烃的寡聚化/多聚化的方法和设备 Pending CN101495429A (zh)

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CN103118777A (zh) * 2010-05-24 2013-05-22 希路瑞亚技术公司 纳米线催化剂
US10654769B2 (en) 2011-05-24 2020-05-19 Siluria Technologies, Inc. Catalysts for petrochemical catalysis
US10780420B2 (en) 2014-05-02 2020-09-22 Lummus Technology Llc Heterogeneous catalysts
US11000835B2 (en) 2014-09-17 2021-05-11 Lummus Technology Llc Catalysts for natural gas processes
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