CN101253135A - 具有改进的排热状况的线型α-烯烃制备方法 - Google Patents

具有改进的排热状况的线型α-烯烃制备方法 Download PDF

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CN101253135A
CN101253135A CNA2006800277982A CN200680027798A CN101253135A CN 101253135 A CN101253135 A CN 101253135A CN A2006800277982 A CNA2006800277982 A CN A2006800277982A CN 200680027798 A CN200680027798 A CN 200680027798A CN 101253135 A CN101253135 A CN 101253135A
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reactor
heat
aforementioned
eliminating medium
linear alpha
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CN101253135B (zh
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P·弗里茨
H·博尔特
K-H·霍夫曼
M·科勒
H-J·赞德
F·莫萨
T·阿里
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Saudi Basic Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

本发明涉及在一种第一有机溶剂和一种均相催化剂的存在下、在一个反应器中将乙烯低聚以制备线型α－烯烃的方法，其特征在于反应器的塔顶馏出物由一种致冷剂冷却。

Description

具有改进的排热状况的线型α-烯烃制备方法
本发明涉及在一种第一有机溶剂和一种均相催化剂的存在下、在一个反应器中将乙烯低聚制备线型α-烯烃(LAO)的方法。
使用有机金属催化剂的乙烯低聚是本领域公知的。低聚反应是高度放热的，因而必须从反应器中除去反应热以防止失控。
DE 43 38 414 C1公开一种制备线型α-烯烃的方法，其中聚合级的乙烯被再循环以除去反应热。因此，乙烯进料(乙烯含量近乎100％，含有少量杂质)在较低温度下被加入反应器中，而未经低聚的单体乙烯在较高温度下除去、冷却并重新加入反应器中。
已发现仅约3％的乙烯进料在低聚过程中被使用，其中剩余部分被用作冷却介质。乙烯相当昂贵。
此外，还发现为达到足够的排热，乙烯冷却循环气体的流速应足够高，这导致对设备、管道、能耗等的要求提高。
根据现有技术的情况，用于低聚乙烯生产线型α-烯烃的反应器中典型的塔顶馏出物温度为约50℃，而反应器底部温度为约60至约100℃。这种情况下，塔顶馏出物的冷却通常由冷却水达到，优选使用冷凝器。基于这些情况和作为适当溶剂的甲苯的应用，少量的甲苯在反应器底部被蒸发，向上流入反应器的塔顶馏出物中，被部分冷凝并作为内回流。这种内部循环只占反应器排热的极小百分比。
因此，本发明的一个目的是提供一种克服了现有技术的缺陷的、通过乙烯的低聚制备线型α-烯烃的方法。尤其应提供这样一种方法，它表现出改进的反应器排热状况，并显著地降低了冷却循环气体的流速，从而节省了设备、管道、能耗等。
所述目的通过一种致冷剂使反应器塔顶馏出物温度冷却而达到。
优选地，所述反应器塔顶馏出物温度维持在约15至约20℃，优选通过冷凝器维持。
更优选地，所述致冷剂是丙烯。
此外，该方法可在至少一种被加入反应器中、在反应器顶部冷凝并在反应器底部再蒸发的冷却介质的存在下实施。
优选地，选择冷却介质以使其在实施该方法时基本保留在反应器中。
在另一个优选的实施方案中，所述冷却介质选自一种大气压下沸点至少为约120℃的惰性第二有机溶剂。
第一有机溶剂可为甲苯。
优选地，所述催化剂包括一种有机酸的锆盐和至少一种有机铝化合物。
可提出锆盐的分子式为ZrCl4-mXm，其中X＝OCOR或OSO3R’，其中R和R’独立地为烷基、烯基或苯基，并且其中0＜m＜4。
所述的至少一种铝化合物可为Al(C2H5)3、Al2Cl3(C2H5)3、AlCl(C2H5)2或其混合物。
最后，所述低聚反应器的底部温度为约60至约100℃。
令人惊奇的是，已发现，通过一种致冷剂冷却反应器塔顶馏出物、优选将反应器塔顶馏出物温度降低至约15至约20℃，显著地促进了内部冷却循环。此外，可减少目前对排热非常重要的大量乙烯进料，并因此可显著降低冷却循环气体的流速。这会进一步节省设备、管道、能耗等。
在一个优选实施方案中，还可将一种合适的冷却介质通入LAO反应器中，这进一步改进了对放热低聚过程产生的热量的排放。选择将要通入反应器——优选注射入反应器——的冷却介质，以使冷却介质可在反应器顶部容易地冷凝，但还应在反应器底部容易地再蒸发。此外，优选将冷却介质在大气压下的沸点选择为使其能够令人满意地避免冷却介质从反应器中排出。
本发明方法可获得直接的内部冷却。
现详细说明本发明的方法。
将溶于适当的溶剂(例如甲苯)中的催化剂加料至低聚反应器中。此外，将乙烯供给至该反应器，并且还可向其中提供一种冷却介质。选择冷却介质以使其可在反应器顶部容易地冷凝，并还可在反应器底部容易地再蒸发。在该反应器中，乙烯发生低聚反应以获得线型α-烯烃。尤其是，当乙烯进料在溶剂和催化剂的混合物中起泡时，乙烯在反应器中进行低聚反应。低聚的产物溶解在溶剂中。该反应器底部温度为约60至约100℃。
反应器塔顶馏出物温度维持在约15至约20℃，优选通过使用致冷剂维持，优选利用冷凝器维持。这样，显著地促进了反应器中的内部冷却循环。通过反应器塔顶馏出物可从反应器中移除乙烯和轻质α-烯烃的混合物，并可将其收集在分离器中。所得到的液体包括溶剂和α-烯烃，可被再循环至反应器中。从分离器出来的仍为气体的部分可在一个冷却装置中被进一步冷却至温度为约5℃，然后被转移至第二分离器中。在冷却装置中对冷却进行调节以使比乙烯重的烯烃液化。然后，所得的线型α-烯烃可以本领域已知的方法进一步处理。未消耗的乙烯可与其新进料混合，再次被通入反应器中。可通过反应器底部上方的一条管线从反应器中排出含有溶剂、催化剂和线型α-烯烃的液体混合物，并且该混合物可以本领域已知的方法进一步处理。
前述说明书、附图或权利要求中所公开的特征，无论以分开的方式还是以任何组合的方式，对于以其不同形式实现本发明而言是重要的。

Claims (11)

1.通过在一种第一有机溶剂和一种均相催化剂的存在下、在一个反应器中将乙烯低聚以制备线型α-烯烃的方法，其特征在于反应器塔顶馏出物由一种致冷剂冷却。
2.权利要求1的方法，其中所述反应器塔顶馏出物的温度维持在约15至约20℃，优选通过一个冷凝器维持。
3.权利要求2的方法，其中所述致冷剂为丙烯。
4.前述任一项权利要求的方法，其中所述方法在至少一种被加入反应器中、在反应器顶部冷凝并在反应器底部再蒸发的冷却介质的存在下实施。
5.权利要求4的方法，其中选择其中所述冷却介质以使其在实施该方法时基本保持在反应器内。
6.权利要求4或5的方法，其中所述冷却介质选自一种大气压下沸点至少为约120℃的惰性第二有机溶剂。
7.前述任一项权利要求的方法，其中所述第一有机溶剂是甲苯。
8.前述任一项权利要求的方法，其中所述催化剂包括一种有机酸的锆盐和至少一种有机铝化合物。
9.权利要求8的方法，其中所述锆盐的分子式为ZrCl4-mXm，其中X＝OCOR或OSO3R’，其中R和R’独立地为烷基、烯基或苯基，并且其中0＜m＜4。
10.权利要求9的方法，其中所述至少一种铝化合物是Al(C2H5)3、Al2Cl3(C2H5)3、AlCl(C2H5)2或其混合物。
11.前述任一项权利要求的方法，其中所述低聚反应器的底部温度为约60至约100℃。
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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010006589A1 (de) 2010-02-02 2011-08-04 Linde Aktiengesellschaft, 80331 Verfahren zur Herstellung linearer a-Olefine
CA2723515C (en) 2010-12-01 2018-05-15 Nova Chemicals Corporation Heat management in ethylene oligomerization
WO2013106771A2 (en) 2012-01-13 2013-07-18 Siluria Technologies, Inc. Process for separating hydrocarbon compounds
US9469577B2 (en) 2012-05-24 2016-10-18 Siluria Technologies, Inc. Oxidative coupling of methane systems and methods
US9969660B2 (en) 2012-07-09 2018-05-15 Siluria Technologies, Inc. Natural gas processing and systems
DE102012014393A1 (de) 2012-07-19 2014-01-23 Linde Aktiengesellschaft Blasensäulenreaktor
AU2013355038B2 (en) 2012-12-07 2017-11-02 Lummus Technology Llc Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
EP3074119B1 (en) 2013-11-27 2019-01-09 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
CN110655437B (zh) 2014-01-08 2022-09-09 鲁玛斯技术有限责任公司 乙烯成液体的系统和方法
EP3097068A4 (en) 2014-01-09 2017-08-16 Siluria Technologies, Inc. Oxidative coupling of methane implementations for olefin production
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
JP6565525B2 (ja) * 2014-09-22 2019-08-28 三菱ケミカル株式会社 α−オレフィン低重合体の製造方法及び製造装置
US9334204B1 (en) 2015-03-17 2016-05-10 Siluria Technologies, Inc. Efficient oxidative coupling of methane processes and systems
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
US9328297B1 (en) 2015-06-16 2016-05-03 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
WO2016205411A2 (en) 2015-06-16 2016-12-22 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
US10513473B2 (en) 2015-09-18 2019-12-24 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US10519077B2 (en) 2015-09-18 2019-12-31 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US20170107162A1 (en) 2015-10-16 2017-04-20 Siluria Technologies, Inc. Separation methods and systems for oxidative coupling of methane
US9944573B2 (en) 2016-04-13 2018-04-17 Siluria Technologies, Inc. Oxidative coupling of methane for olefin production
US20180169561A1 (en) 2016-12-19 2018-06-21 Siluria Technologies, Inc. Methods and systems for performing chemical separations
ES2960342T3 (es) 2017-05-23 2024-03-04 Lummus Technology Inc Integración de procedimientos de acoplamiento oxidativo del metano
US10836689B2 (en) 2017-07-07 2020-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
US11667590B2 (en) 2021-05-26 2023-06-06 Chevron Phillips Chemical Company, Lp Ethylene oligomerization processes

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2351123A (en) * 1940-05-20 1944-06-13 Phillips Petroleum Co Process for preparing hydrocarbons for polymerization
DE3844180A1 (de) 1988-12-29 1990-07-05 Hoechst Ag Verfahren zur abtrennung fluechtiger bestandteile aus durch hochdruckpolymerisation erhaltenen reaktionsgemischen
FR2693455B1 (fr) 1992-07-09 1994-09-30 Inst Francais Du Petrole Procédé de fabrication d'oléfines alpha légères par oligomérisation de l'éthylène.
DE4338414C1 (de) * 1993-11-10 1995-03-16 Linde Ag Verfahren zur Herstellung linearer Olefine
FR2715154B1 (fr) 1994-01-14 1996-04-05 Inst Francais Du Petrole Procédé de production d'oléfines alpha légères de pureté améliorée par oligomérisation, de l'éthylène.
US5811608A (en) 1995-12-15 1998-09-22 Uop Llc Process for oligomer production and saturation
FR2748018B1 (fr) 1996-04-26 1998-06-26 Inst Francais Du Petrole Procede ameliore de conversion de l'ethylene en olefines alpha legeres avec utilisation d'additifs a base de sels d'ammonium quaternaire
FR2759922B1 (fr) 1997-02-25 1999-05-07 Inst Francais Du Petrole Composition catalytique amelioree pour la conversion de l'ethylene en olefines alpha legeres
DE19910103A1 (de) 1999-03-08 2000-09-14 Basf Ag Verfahren zur Oligomerisierung von C¶6¶-Olefinen
JP2002256007A (ja) 2000-12-26 2002-09-11 Idemitsu Petrochem Co Ltd α−オレフィン低重合体の製造方法
EP1542946A1 (en) 2002-09-25 2005-06-22 Shell Internationale Researchmaatschappij B.V. Process for making a linear alpha-olefin oligomer using a heat exchanger
RU2312848C2 (ru) * 2002-09-25 2007-12-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения олигомера линейного альфа-олефина и установка для его осуществления с использованием теплообменника
CN102615734B (zh) * 2004-08-27 2014-07-02 切夫里昂菲利普化学有限责任公司 能量有效的聚烯烃方法

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US9012577B2 (en) 2015-04-21
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