CN1061021C - 在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法 - Google Patents
在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法 Download PDFInfo
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- 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
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Abstract
在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法。催化剂由一种羧酸锆和一种有机金属化合物组成。为了结束其低聚能力,在乙烯转化成α-烯烃后,必须马上钝化催化剂。这通过添加脂肪酸来完成。通过氧化铝凝胶吸附从反应混合物中除去催化剂后,随后用水冲洗并萃取回收脂肪酸。
Description
本发明涉及一种在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法,其中通过向反应混合物中添加一种有机氧化合物,特别是一种脂肪酸,来钝化由一种羧酸锆和一种有机金属化合物组成的液体催化剂,随后通过用可再生的氧化铝凝胶吸附将其从混合物中分离出来。
线性α-烯烃,例如含4至8个碳原子的线性α-烯烃,是被例如广泛用作聚烯烃改性用共聚单体或用作制备增塑剂、表面活性物质及类似物的原料并被大量使用的化合物。
由IT-A-24498A/79已知,乙烯在液相低聚成线性α-烯烃。该反应在稍为提高的温度和压力下于有机溶剂(例如甲苯、苯或庚烷)中进行。在溶剂中溶入一种由两组分,即一种有机酸的锆盐和一种有机铝化合物组成的催化剂。该已知催化剂含有式Zr(OCOR)4或Zr(OSO3R′)4的有机酸的锆盐作为锆化合物,式中R和R′为烷基、烯基或苯基。第二组分由烷基倍半氯化铝组成。
在液相中使用该催化剂时工艺技术上的问题在于,要在所希望的时刻,例如反应混合物从反应器中流出不久,中断乙烯的低聚反应,以便不出现不希望的导致无用副产物的副反应。
在UdSSR发明者证书1118038和1573785中,该问题已经初步得到解决。与IT-A-24498A/79的描述基本相同,在该发明者证书的方法中,通过添加化学计量的醇来破坏催化剂。尔后将反应混合物送到大表面积的吸附剂上,以便从反应混合物中分离铝、锆及其络合物。作为吸附剂,提议用颗粒物质(硅胶、粘土、沸石)、锯末和其它物质。然而,已证明该已知方法的缺点是,必须非常谨慎地将醇与其它组分分离,因为醇继续留在低聚溶剂中可能会有破坏作用。在已知方法中用蒸汽再生吸附剂并重新使用该吸附剂。
结束催化剂活性的另一种途径如US-A-4486615的方法所述。那里通过添加羧酸来终止催化剂的活性。这通常需要从外面加入工艺中,因而又是一种不可忽略的开支。
本发明的目的是,提出一种在制备α-烯烃的低聚过程中钝化催化剂的方法,该方法极其有效且不需要另外添加化学品。
按照本发明,该目的的解决方案是,通过用水冲洗来再生氧化铝凝胶,用一种有机溶剂从水相萃取催化剂锆组分的羧酸根生成的脂肪酸,随后将其用于催化剂钝化。
具体地,本发明提供了一种在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法,其中通过向反应混合物添加一种脂肪酸来钝化由一种羧酸锆和一种有机金属化合物组成的液体催化剂,此后通过用可再生的氧化铝凝胶吸附从混合物中分离催化剂,其特征是,通过用水冲洗来再生氧化铝凝胶,用一种有机溶剂从水相萃取由催化剂锆组分的羧酸根生成的脂肪酸,接着将该脂肪酸用于钝化催化剂。
本发明的方法具有一系列优点。
由于用水冲洗吸附剂,因而是一种非常廉价的工艺方式。冲洗时形成的脂肪酸可以说是吸附剂再生的一种副效应,本发明用它来破坏催化剂的活性。以这种方式由工艺本身产生所需的脂肪酸并循环使用。简单地用合适的有机溶剂萃取即可实现从冲洗的水相分离出脂肪酸。考虑到经济原因,这里建议使用与低聚反应相同的溶剂,即大多数情况下用甲苯。
另外,吸附时还分开了两种元素锆和铝。锆以ZrO2形式沉淀在吸附剂上,而烷基倍半氯化铝过滤成氯氧化铝,用水相即可将其分离。
具体假设发生了以下过程:
活性低聚催化剂的结构可能是M-C2H5(M=金属)。链增长估计在M-C2H5单元上进行。
用脂肪酸钝化催化剂时,M-C2H5单元可能这样被破坏:
锆化合物与水的进一步反应如下图:
如上所述,ZrO2沉淀在吸附剂上,而脂肪酸用于催化剂钝化。
然后,按下图进行附在吸附剂上的乙基倍半氯化铝的羟基化:
如上所述,这里形成的氧氯化物在水相溶解。该溶液只含有铝作为金属组分,也就是说不含重金属,所以中和后不用其它处理步骤即可送入下水道。需要时也可在浓缩后用冶金学方法回收铝。
以ZrO2形式留在吸附剂上的锆不妨碍此后的催化剂分离,因为ZrO2本身有很好的吸附性能。在更换用过的氧化铝凝胶物料时,可用冶金方法回收锆。这样的工艺当氧化铝凝胶上的Zr浓度超过了3%(重量)时是经济的。
用氧化铝凝胶分离催化剂时,本发明的方法在工艺操作方面是很灵活的:压力和温度对催化剂分离的效率实际上没有影响。
已证明含4至8个C碳原子的脂肪酸的酯特别适合用作羧酸根。磺酸酯也可用于本发明的催化剂。
下面借助于一个实施例进一步说明本发明。
在31巴压力和80℃温度下由一个低聚反应器排出总量为20,429kg/h的反应混合物。该混合物含有作为催化剂组分的11kg/hZr(OCOR)4和24kg/h Al2Cl3(C2H5)3。靠紧反应器出口处添加溶入192kg/h甲苯中的36kg/h脂肪酸以钝化催化剂。
接着将含有失活催化剂的低聚物送入吸附器中,于约31巴和75℃吸附催化剂组分。
吸附器装有50m3氧化铝凝胶,预计吸附时间为170小时(操作)。吸附时间结束后,在2巴和75℃用28,000kg/h水冲洗吸附器一小时,进行再生,这时由催化剂锆组分的有机配位体形成脂肪酸。用192kg/h甲苯从水中萃取该脂肪酸并用于催化剂钝化。
Claims (2)
1、在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法,其中通过向反应混合物添加一种脂肪酸来钝化由一种羧酸锆和一种有机金属化合物组成的液体催化剂,此后通过用可再生的氧化铝凝胶吸附从混合物中分离催化剂,其特征是,通过用水冲洗来再生氧化铝凝胶,用一种有机溶剂从水相萃取由催化剂锆组分的羧酸根生成的脂肪酸,接着将该脂肪酸用于钝化催化剂。
2、按权利要求1所述的方法,其特征是,用甲苯作有机溶剂。
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Application Number | Priority Date | Filing Date | Title |
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DE4338415A DE4338415C1 (de) | 1993-11-10 | 1993-11-10 | Verfahren zur Katalysatordesaktivierung bei der katalytisch beschleunigten Herstellung linearer Alpha-Olefine durch Oligomerisierung von Ethylen |
DEP4338415.3 | 1993-11-10 |
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CN1108153A CN1108153A (zh) | 1995-09-13 |
CN1061021C true CN1061021C (zh) | 2001-01-24 |
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CN94118707A Expired - Fee Related CN1061021C (zh) | 1993-11-10 | 1994-11-08 | 在催化加速乙烯低聚制备线性α-烯烃时钝化催化剂的方法 |
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Families Citing this family (6)
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EP1752433B1 (en) * | 2005-08-10 | 2012-10-03 | Linde AG | Improved drying process for linear alpha-olefins |
EP1754694A1 (en) * | 2005-08-10 | 2007-02-21 | Linde AG | Method for deactivation and removal of catalytic components in the oligomerisation of ethylene |
DE602005014647D1 (de) * | 2005-10-19 | 2009-07-09 | Linde Ag | Verfahren zur Oligomerisierung und/oder Polymerisierung von Ethylen mittels Spülen der Anlage und der Rohre |
EP2354113A1 (en) * | 2010-02-04 | 2011-08-10 | Linde AG | Method for deactivation of a catalyst |
RU2471762C1 (ru) * | 2011-06-22 | 2013-01-10 | Открытое акционерное общество "СИБУР Холдинг" (ОАО "СИБУР Холдинг") | Способ выделения продуктов олигомеризации олефинов и разложения остатков катализатора олигомеризации |
CN107207382B (zh) * | 2014-12-23 | 2021-06-18 | 公共型股份公司希布尔控股 | 在烯烃低聚反应中使聚合物和减活的有机金属催化剂沉淀的方法 |
Citations (4)
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---|---|---|---|---|
US4434312A (en) * | 1978-03-02 | 1984-02-28 | Exxon Research And Engineering Co. | Preparation of linear olefin products |
US4486615A (en) * | 1960-09-14 | 1984-12-04 | Exxon Research & Engineering Co. | Preparation of linear olefin products |
JPS62430A (ja) * | 1985-06-26 | 1987-01-06 | Idemitsu Petrochem Co Ltd | 線状α−オレフインの製造方法 |
JPH03103406A (ja) * | 1989-09-14 | 1991-04-30 | Idemitsu Petrochem Co Ltd | 線状α―オレフィンの製造方法 |
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SU1118038A1 (ru) * | 1983-04-16 | 1999-03-27 | В.Н. Мельников | Способ очистки продуктов олигомеризации и димеризации этилена от остатков отработанного катализатора |
SU1573785A1 (ru) * | 1988-04-28 | 1999-03-27 | В.Н. Мельников | Способ очистки продуктов ди- и олигомеризации олефинов от остатков отработанного каталитического комплекса |
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- 1993-11-10 DE DE4338415A patent/DE4338415C1/de not_active Expired - Fee Related
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4486615A (en) * | 1960-09-14 | 1984-12-04 | Exxon Research & Engineering Co. | Preparation of linear olefin products |
US4434312A (en) * | 1978-03-02 | 1984-02-28 | Exxon Research And Engineering Co. | Preparation of linear olefin products |
JPS62430A (ja) * | 1985-06-26 | 1987-01-06 | Idemitsu Petrochem Co Ltd | 線状α−オレフインの製造方法 |
JPH03103406A (ja) * | 1989-09-14 | 1991-04-30 | Idemitsu Petrochem Co Ltd | 線状α―オレフィンの製造方法 |
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