CN101018605A - 改进的用于生产直链α－烯烃的助催化剂 - Google Patents

改进的用于生产直链α－烯烃的助催化剂 Download PDF

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CN101018605A
CN101018605A CNA2005800281540A CN200580028154A CN101018605A CN 101018605 A CN101018605 A CN 101018605A CN A2005800281540 A CNA2005800281540 A CN A2005800281540A CN 200580028154 A CN200580028154 A CN 200580028154A CN 101018605 A CN101018605 A CN 101018605A
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aluminium
linear alpha
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CN100446860C (zh
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H·博尔特
P·M·弗里茨
H·哈纳
A·阿拉卡巴
M·扎胡
F·莫萨
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Saudi Basic Industries Corp
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本发明涉及一种由有机酸的锆盐和助催化剂组成的用于通过乙烯低聚反应生成直链α－烯烃的均相催化剂，所述助催化剂由烷基铝和/或氯化铝组成。可通过将助催化剂中氯与铝的摩尔比在1.0至1.5的范围内调整，从而在某些时候大幅度提高催化剂体系的活性。提高了生产工艺的经济可行性和产物纯度。

Description

改进的用于生产直链α-烯烃的助催化剂
本发明涉及一种由有机酸的锆盐和助催化剂组成的、用于通过乙烯的低聚反应制造直链α-烯烃的均相催化剂。
直链α-烯烃(LAO)，例如具有4至30个碳原子的直链α-烯烃，是例如作为用于聚烯烃改性的共聚单体或作为制造增塑剂、家用清洁剂、浮选剂、乳化剂、钻孔液体、表面活性物质和合成油、腻子、密封剂等的原料而广泛应用且需求量大的化合物。
根据USSR发明人证书1042701A、未授权的意大利专利申请ITA24498A/79和德国专利DE4338414及DE4338416中所述的发明，乙烯低聚为C4-C30 LAO的反应在60至80℃、压力为2.0至4.0MPa的条件下在有机溶剂中进行。甲苯、苯或庚烷用作反应介质。上述所有方法均使用由有机酸的锆盐以及选自烷基铝Al(C2H5)3、Al2Cl3(C2H5)3或AlCl(C2H5)2之一的助催化剂组成的催化剂。为避免发生不想要的副反应，需要在反应混合物离开反应器之后立刻终止低聚反应。通过向反应混合物中加入极性氧化合物(H2O、甲醇、乙醇、羧酸等)使催化剂失活，再通过将催化剂吸附到可再生的氧化铝凝胶上将催化剂从混合物中分离。失活的催化剂必须被新鲜催化剂代替。
锆盐的高价格意味着催化剂占据了工艺的操作成本中相当的比例。催化剂更高的活性(以kg LAO产物/g Zr表示)导致更低的消耗并且进而由于操作成本的降低以及随之而来可能的贮存、分配、去活和去除催化剂的设备的尺寸减小而导致的资本成本的降低，从而提高了LAO生产的经济可行性。
因此本发明的一个目的是通过改变目前用于LAO生产的催化剂的化学组成，从而以降低催化剂消耗而不使产品质量下降的方式提高其活性。
根据本发明，通过制成烷基铝和/或氯化铝的混合物形式的助催化剂达到了这一目的，其中可通过改变混合物中各种化合物的比例而将助催化剂中的氯与铝的摩尔比在一定范围内任意调整。
DE4338414描述了一种可方便地与该文献所述工艺结合使用的催化剂体系。锆化合物具有化学式ZrClmXn，其中m+n＝4.0≤m≤2且X表示由C4至C9的脂肪酸衍生的羧化物。已经证实化合物Al2Cl3(C2H5)3是一种实践中尤其有利的助催化剂，可产生10kg(LAO)/g(Zr)的催化剂活性。
现已发现，确定催化剂活性水平的决定性的参数为助催化剂中氯与铝的摩尔比。如果适当地选择了该比例，则可获得显著高于10kg(LAO)/g(Zr)的数值。同时也提高了产物纯度。
助催化剂优选由物质Al(C2H5)3和/或AlCl(C2H5)2和/或Al2Cl3(C2H5)3和/或AlCl2(C2H5)和/或(AlCl3)混合以使得Cl∶Al比为1.0至1.5之间的数值。Cl∶Al比尤其优选为1.0至1.3之间的数值。
图中绘出了催化剂活性随助催化剂中Cl∶Al比变化的曲线。从Cl∶Al比为1.5——对应于现有技术(Al2Cl3(C2H5)3)——时的活性为10kg(LAO)/g(Zr)开始，活性随着比值的降低迅速上升，直到Cl∶Al＝1.26时比现有技术高约500％。然后活性缓慢降至Cl∶Al＝1.02时的约54kg(LAO)/g(Zr)。如果采用高于1.5的Cl∶Al比，则活性降低。当Cl∶Al＝1.77时，活性仅为3.1kg(LAO)/g(Zr)。

Claims (4)

1.一种由有机酸的锆盐和助催化剂组成的用于通过乙烯低聚反应生成直链α-烯烃的均相催化剂，其特征在于制成烷基铝和/或氯化铝的混合物形式的助催化剂，其中可通过改变混合物中各种化合物的比例而将助催化剂中的氯与铝的摩尔比在一定范围内任意调整。
2.权利要求1的催化剂，其特征在于制成烷基铝Al(C2H5)3和/或AlCl(C2H5)2和/或Al2Cl3(C2H5)3和/或AlCl2(C2H5)和/或氯化铝(AlCl3)的混合物形式的助催化剂。
3.权利要求1或2的催化剂，其特征在于助催化剂中氯与铝的比调整到1.0至1.5之间的一个数值。
4.权利要求1或2的催化剂，其特征在于助催化剂中氯与铝的比调整到1.0至1.3之间的一个数值。
CNB2005800281540A 2004-08-20 2005-07-07 改进的用于生产直链α-烯烃的助催化剂 Active CN100446860C (zh)

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DE602006008931D1 (de) * 2006-07-31 2009-10-15 Linde Ag Verfahren zur Oligomerisierung von Ethylen und/oder alpha-Olefinen
ES2913079T3 (es) * 2014-07-18 2022-05-31 Sabic Global Technologies Bv Composición catalizadora y proceso para preparar alfa-olefinas lineales
US10519077B2 (en) 2015-09-18 2019-12-31 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US10513473B2 (en) 2015-09-18 2019-12-24 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US11667590B2 (en) 2021-05-26 2023-06-06 Chevron Phillips Chemical Company, Lp Ethylene oligomerization processes

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US3862257A (en) * 1972-04-17 1975-01-21 Exxon Research Engineering Co Modified ziegler catalyst for alpha olefin wax synthesis
US4434312A (en) 1978-03-02 1984-02-28 Exxon Research And Engineering Co. Preparation of linear olefin products
US4966874A (en) 1988-05-18 1990-10-30 Exxon Chemical Patents Inc. Process for preparing linear alpha-olefins using zirconium adducts as catalysts
US5449850A (en) * 1991-03-12 1995-09-12 Exxon Chemical Patents Inc. Process for oligomerizing C3 and higher olefins using zirconium adducts as catalysts (CS-467)
FR2689500B1 (fr) 1992-04-01 1994-06-10 Inst Francais Du Petrole Procede d'oligomerisation de l'ethylene en olefines alpha legeres.
RU2117012C1 (ru) 1997-06-26 1998-08-10 Институт химической физики в Черноголовке РАН Каталитическая система для олигомеризации этилена в линейные альфа-олефины.
US6930218B2 (en) 2001-01-23 2005-08-16 Indian Petrochemicals Corporation Limited Process for the preparation of linear low molecular weight olefins by the oligomerization of ethylene

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RU2368419C2 (ru) 2009-09-27
US20080176738A1 (en) 2008-07-24
ZA200701435B (en) 2008-06-25
KR20070052763A (ko) 2007-05-22
MY142446A (en) 2010-11-30
JP2008510599A (ja) 2008-04-10
EP1778399A1 (en) 2007-05-02
KR101102652B1 (ko) 2012-01-04
ATE534463T1 (de) 2011-12-15
BRPI0514486B1 (pt) 2015-06-09
MX2007001625A (es) 2007-06-25
EP1778399B1 (en) 2011-11-23
CA2574231C (en) 2011-09-06
BRPI0514486A (pt) 2008-06-17
ES2375967T3 (es) 2012-03-07
CN100446860C (zh) 2008-12-31
RU2007110175A (ru) 2008-09-27

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