CN102264473B - 离子液体催化剂的再循环 - Google Patents

离子液体催化剂的再循环 Download PDF

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CN102264473B
CN102264473B CN2009801520053A CN200980152005A CN102264473B CN 102264473 B CN102264473 B CN 102264473B CN 2009801520053 A CN2009801520053 A CN 2009801520053A CN 200980152005 A CN200980152005 A CN 200980152005A CN 102264473 B CN102264473 B CN 102264473B
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S·I·霍梅尔托夫特
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Abstract

提供了一种安全输送或再循环基于氯铝酸盐的离子液体催化剂的方法。该方法包括将仲醇与基于氯铝酸盐的离子液体混合并使得发生反应生成氯化铝加合物沉淀。将沉淀过滤并除去仲醇，留下固体盐。该固体盐是不存在氯化铝的离子液体催化剂，例如，正丁基吡啶鎓氯化物。将该盐再循环到反应器。在引入到反应器中之前将AlCl3加入到该盐中以重新制得离子液体催化剂，例如正丁基吡啶鎓七氯铝酸盐。

Description

离子液体催化剂的再循环
技术领域
本发明涉及再生离子液体催化剂的再循环(recycling)。更具体地，本发明涉及离子液体催化剂的卤化物盐的再循环。
背景技术
离子液体是全部由离子组成的液体。所谓的“低温”离子液体通常是熔点低于100℃或者甚至常常低于室温的有机盐。离子液体可适合例如在烷基化中用作催化剂和用作溶剂。一类离子液体是熔融盐组合物，它们在低温下熔融，并用作催化剂、溶剂和电解质。这种组合物是组分的混合物，该混合物在低于各组分的各自熔点的温度下为液体。
离子液体可以定义为这样的液体，该液体的组成完全由作为阳离子和阴离子的结合的离子组成。最常见的离子液体是由有机基的阳离子和无机或有机阴离子制备的那些。最常见的有机阳离子是铵阳离子，但也经常使用磷鎓阳离子和锍阳离子。吡啶鎓和咪唑鎓的离子液体也许是最常用的阳离子。阴离子包括，但不限于，BF4-、PF6-、卤铝酸根例如Al2Cl7-和Al2Br7-、[(CF3SO2)2N]-、烷基硫酸根(RSO3-)、羧酸根(RCO2-)和许多其它阴离子。催化上最让人感兴趣的离子液体是衍生自卤化铵和路易斯酸(例如AlCl3、TiCl4、SnCl4、FeCl3...等)的那些。氯铝酸盐离子液体也许是最常用的离子液体催化剂体系。
这类低温离子液体或熔融盐的实例是氯铝酸盐。例如，烷基咪唑鎓或吡啶鎓盐可以与三氯化铝(AlCl3)混合生成熔融的氯铝酸盐。美国专利4,122,245讨论了1-烷基吡啶鎓氯化物和三氯化铝的熔融盐作为电解质的用途。讨论了以来自三氯化铝和烷基咪唑鎓卤化物的熔融盐作为电解质的用途的其它专利是美国专利4,463,071和4,463,072。美国专利5,104,840描述了包含至少一种二卤化烷基铝和至少一种季铵卤化物和/或至少一种季铵磷鎓卤化物的离子液体和它们作为溶剂在催化反应中的用途。
美国专利No.6,096,680描述了液体包合物组合物，其在Friedel-Craft反应中用作可重复使用的铝催化剂。在一个实施方案中，该液体包合物组合物由多种组分生成，所述组分包括：(i)至少一种三卤化铝，(ii)至少一种盐，所述盐选自碱金属卤化物、碱土金属卤化物、碱金属拟卤化物、季铵盐、季磷鎓盐、或三元锍盐、或上述中任意两种或更多种的混合物，和(iii)至少一种芳烃化合物。含铝催化剂是用于Friedel-Craft反应的最常见的路易斯酸催化剂之一。Friedel-Craft反应是属于包括烷基化反应在内的更宽范畴的亲电取代反应的反应。
离子液体及其制备方法的其它实例也可以在美国专利No.5,731,101；6,797,853以及在美国专利申请公开2004/0077914和2004/0133056中找到。
使用的结果是离子液体催化剂变得失活，即丧失活性，并且可能最终需要更换。利用离子液体催化剂的烷基化方法生成称作混合聚合物的副产物。这些混合聚合物通过与离子液体催化剂形成络合物而使离子液体催化剂失活。混合聚合物是高度不饱和分子。随着混合聚合物浓度提高，离子液体催化剂的活性变得受到削弱或至少受到危害。混合聚合物还可以变得被氯化并可以通过它们的氯基团与三氯化铝相互作用，且因此降低催化剂的总体活性或减小其作为催化剂用于预期目的例如烷基化的有效性。混合聚合物所致的离子液体催化剂失活不仅对于烷基化化学反应具有问题，而且在很大程度上对使用离子液体的经济性具有影响，这是因为它们是昂贵的催化体系并且它们的频繁更换将是高花费的。因此，烷基化过程中的离子液体催化剂的商业开发除非它们有效地得以再生和再循环才是有可能的。
设计了从酸性离子液体催化剂除去混合聚合物以使催化剂再生的各种方法。例如，参见美国专利申请公开2007/0142213。
一旦使离子液体催化剂再生，通常将该催化剂再循环到主反应中。遗憾的是，离子液体催化剂对空气和水分非常敏感。除非再循环系统绝对干燥并且不含有氧，该催化剂可受到损害。因此，虽然设计了多种方法使离子液体催化剂再生，但是在工业上仍非常需要安全输送/再循环该催化剂的方法。
概述
提供了一种安全输送或再循环基于氯铝酸盐的离子液体催化剂的方法。该方法包括将仲醇与基于氯铝酸盐的离子液体混合并使得发生反应生成氯化铝加合物沉淀。将沉淀过滤并除去仲醇，留下固体盐。该固体盐是不存在氯化铝的离子液体催化剂，例如正丁基吡啶鎓氯化物。将该盐再循环到反应器。在引入到反应器中之前将AlCl3加入到该盐中以重新制得离子液体催化剂，例如正丁基吡啶鎓七氯铝酸盐。
除其它因素外，发现输送或再循环离子液体盐比输送或再循环离子液体催化剂要容易和安全得多。所述盐不像所述催化剂对空气和水分敏感，因此可更加容易地进行输送。本发明使用仲醇使氯化铝沉淀的方法提供了除去氯化铝并且获得用于循环或其它输送的离子液体盐的快速且有效的方法。
详述
本发明的方法是有关基于氯铝酸盐的离子液体催化剂的安全且有效的输送或再循环。发现通过使基于氯铝酸盐的离子液体催化剂与仲醇反应，催化剂中的氯化铝与仲醇形成络合物。
该络合物从溶液沉淀出并且可通过过滤除去。通过除去仲醇例如通过煮去该醇并且留下作为固体的氯化物盐来回收离子液体催化剂中的剩余氯化物盐。然后可将该固体盐输送到反应器，其中在引入到反应器中之前将AlCl3加入到所述盐中可形成催化剂。
离子液体催化剂可以是基于氯铝酸盐的任何离子液体。离子液体催化剂的一个实施例是胺系阳离子物质混合氯化铝如1-烷基-吡啶鎓氯铝酸盐，例如1-丁基-吡啶鎓七氯铝酸盐。优选的离子液体催化剂选自：包含下面通式A的烃基取代吡啶鎓卤化物和三氯化铝、或者下面通式B的烃基取代咪唑鎓卤化物和三氯化铝的氯铝酸盐离子液体催化剂，优选1摩尔当量的分别为通式A和B的烃基取代吡啶鎓卤化物或烃基取代咪唑鎓卤化物对应于2摩尔当量的三氯化铝；包含下面通式A的烷基取代吡啶鎓卤化物和三氯化铝、或者下面通式B的烷基取代咪唑鎓卤化物和三氯化铝的氯铝酸盐离子液体催化剂，优选1摩尔当量的分别为通式A和B的烷基取代吡啶鎓卤化物或烷基取代咪唑鎓卤化物对应于2摩尔当量的三氯化铝；以及它们的混合物，
Figure BDA0000070448260000041
其中R＝H、甲基、乙基、丙基、丁基、戊基、己基或苄基，基团R′和R″＝H、甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸根，优选氯铝酸根，R1和R2＝H、甲基、乙基、丙基、丁基、戊基、己基或苄基，其中R1和R2可以相同或不同。
离子液体催化剂的另一个实例是与三氯化铝混合的通式C的烷基取代卤化铵；
其中R＝H、甲基、乙基、丙基、丁基、戊基、己基或苄基；R1、R2和R3＝甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸盐。
含有Al2Cl7或AlCl4的离子液体也可以是合适的。当基于氯铝酸盐的这种离子液体需要输送或再循环时可使用本发明的方法。通常，该方法特别应用于离子液体催化剂在烃转化反应中废掉后再生之后。一种这样的反应是烷基化反应。
对于使废离子液体催化剂再生，已知有多种方法。例如，参见美国专利申请公开2007/0142213，以及美国序列No.12/003,578和12/003,577，通过引用将它们以其全文并入本文。这些方法可除去混合(conjoint)聚合物并且提供再生的离子液体催化剂。
一旦使该催化剂再生，并且该催化剂准备进行输送或再循环，则将该催化剂与仲醇混合。所述仲醇可以是异丙醇、2-丁醇、2-己醇、2-庚醇或与AlCl3形成加合物并且该加合物具有允许其形成沉淀的溶解性的任何合适的仲醇。异丙醇优选作为所述仲醇，这是因为发现其在与AlCl3产生形成沉淀的加合物中最为有效。异丙醇还允许容易地除去从而回收离子液体盐。
将所形成的沉淀从溶液过滤除去。然后例如通过仲醇的煮去/蒸发除去该醇。仲醇的去除留下作为固体盐的离子液体催化剂的氯化物盐。通常，离子液体催化剂的氯化物盐是固体盐。通常，该氯化物盐还将含有一些没有形成加合物的AlCl3，或加合物残留在溶液中。大于90％的AlCl3通常随加合物一起分离出，溶液中留下不大于10％。以溶解的加合物留在溶液中的AlCl3的量可通过冷却该溶液进一步降低。温度越低，通常将沉淀出越多的AlCl3加合物。留在溶液中的AlCl3的量可以降低至6％、5％或甚至更小。
然后可将固体氯化物盐输送到反应器或储罐而没有在使离子液体催化剂本身再循环时所存在的有关暴露于空气的问题。一旦需要所述盐作为催化剂，则在引入到反应器中之前将AlCl3加入到所述盐中可重新生成催化剂。该重生(reformation)可在储罐中、重生罐中或恰在引入到反应器之前进行。
提供以下实施例进一步描述本发明方法的实施方案。它们仅是说明性的，并非限制性的。
实施例
在50-60℃下将5ml(约6.7gm)正丁基吡啶鎓七氯铝酸盐注入到55ml异丙醇中，并且维持搅拌15分钟。1分钟后该溶液变得不透明并且开始生成一些沉淀。然后将该混合物冷却至约20℃并过滤出白色沉淀。在氮气中干燥该固体从而得到10.36g白色粉末，其中7.65％的铝含量相应于0.80g Al。将所述溶液浓缩至干从而得到3.27g黄色结晶固体，该固体含有1.63％Al(相应于0.05g)。因此，一旦除去异丙醇，94％的铝随着白色固体沉淀被除去，从而在回收的盐中仅剩下6％。
在较低的温度例如0℃以下的沉淀通常将产生甚至更好的分离，因此在回收的盐中铝含量更低。然而，如果仅仅将所述盐再循环到反应工艺，该工艺中将AlCl3加入到所述盐中以重新生成离子液体催化剂，则铝含量的进一步降低可以是不必要的。
因此，本发明方法提供了一种安全输送离子液体催化剂的盐的简单方法，所述盐在后来可用于重新生成所述催化剂。该方法对于在炼厂中原位进行是足够简单的。白色沉淀加合物在水中高度可溶并且可以作为水溶液进行处理或者作为化学品输出或者用于其它化学工艺。
虽然描述了与其优选实施方案有关的本发明，但本领域技术人员应意识到可以做出没有具体描述的增加、删除、修改和替代，并同时不脱离如所附权利要求书中所限定的本发明的精神和范围。

Claims (26)

1.一种用于制备基于氯铝酸盐的离子液体的盐的方法，该方法包括将基于氯铝酸盐的离子液体与仲醇混合并形成氯化铝加合物沉淀，
除去该沉淀；和
除去仲醇从而留下所述离子液体的盐。
2.根据权利要求1的方法，其中所述离子液体选自：
第一氯铝酸盐离子液体，其包含通式A的烃基取代吡啶鎓卤化物和三氯化铝、或者通式B的烃基取代咪唑鎓卤化物和三氯化铝；
第二氯铝酸盐离子液体，其包含通式A的烷基取代吡啶鎓卤化物和三氯化铝、或者通式B的烷基取代咪唑鎓卤化物和三氯化铝；
以及它们的混合物，
其中所述通式A和通式B由下面的结构表示：
Figure FDA00003197188200011
其中R=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，基团R'和R''=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸根，R1和R2=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，其中R1和R2可以相同或不同。
3.根据权利要求2的方法，其中所述第一氯铝酸盐离子液体催化剂通过将1摩尔当量的烃基取代吡啶鎓卤化物或烃基取代咪唑鎓卤化物与2摩尔当量的三氯化铝混合来进行制备。
4.根据权利要求2的方法，其中所述第二氯铝酸盐离子液体催化剂通过将1摩尔当量的烷基取代吡啶鎓卤化物或烷基取代咪唑鎓卤化物与2摩尔当量的三氯化铝混合来进行制备。
5.根据权利要求1的方法，其中所述离子液体是通式C的烷基取代卤化铵和三氯化铝，
Figure FDA00003197188200021
其中R=H、甲基、乙基、丙基、丁基、戊基、己基或苄基；R1、R2和R3=甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸根。
6.根据权利要求1的方法，其中所述离子液体是N-丁基吡啶鎓七氯铝酸盐。
7.根据权利要求6的方法，其中所述离子液体的卤化物盐是N-丁基吡啶鎓氯化物。
8.根据权利要求1的方法，其中所述混合在室温或更低的温度下进行。
9.根据权利要求8的方法，其中所述混合在20℃或更低的温度下进行。
10.根据权利要求1的方法，其中所述仲醇是异丙醇。
11.根据权利要求1的方法，其中所述离子液体是催化剂。
12.根据权利要求11的方法，其中所述方法还包括将卤化物盐再循环到反应器，并且在将所述卤化物盐引入到反应器中之前将AlCl3加入到该卤化物盐以重新制得催化剂。
13.根据权利要求12的方法，其中所述反应器是烷基化反应器。
14.一种输送基于氯铝酸盐的离子液体催化剂的方法，该方法包括：
将基于氯铝酸盐的离子液体与仲醇混合并形成氯化铝加合物沉淀，
除去该沉淀，
除去仲醇从而留下离子液体的盐，并将该盐输送到所选择的目的地。
15.根据权利要求14的方法，该方法还包括在目的地将三氯化铝加入到所述离子液体的盐中以重新生成离子液体。
16.根据权利要求15的方法，其中所述目的地是烷基化反应器并且在将离子液体引入到该反应器之前重新生成。
17.根据权利要求14的方法，其中所述离子液体选自：
第一氯铝酸盐离子液体，其包含通式A的烃基取代吡啶鎓卤化物和三氯化铝、或者通式B的烃基取代咪唑鎓卤化物和三氯化铝；
第二氯铝酸盐离子液体，其包含通式A的烷基取代吡啶鎓卤化物和三氯化铝、或者通式B的烷基取代咪唑鎓卤化物和三氯化铝；
以及它们的混合物，
其中所述通式A和通式B由下面的结构表示：
Figure FDA00003197188200031
其中R=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，基团R'和R''=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸根，R1和R2=H、甲基、乙基、丙基、丁基、戊基、己基或苄基，其中R1和R2可以相同或不同。
18.根据权利要求17的方法，其中所述第一氯铝酸盐离子液体催化剂通过将1摩尔当量的烃基取代吡啶鎓卤化物或烃基取代咪唑鎓卤化物与2摩尔当量的三氯化铝组合来进行制备。
19.根据权利要求17的方法，其中所述第二氯铝酸盐离子液体催化剂通过将1摩尔当量的烷基取代吡啶鎓卤化物或烷基取代咪唑鎓卤化物与2摩尔当量的三氯化铝组合来进行制备。
20.根据权利要求14的方法，其中所述离子液体是通式C的烷基取代卤化铵和三氯化铝，
Figure FDA00003197188200041
其中R=H、甲基、乙基、丙基、丁基、戊基、己基或苄基；R1、R2和R3=甲基、乙基、丙基、丁基、戊基、己基或苄基，X为卤铝酸根。
21.根据权利要求14的方法，其中所述离子液体是N-丁基吡啶鎓七氯铝酸盐。
22.根据权利要求21的方法，其中所述离子液体的卤化物盐是N-丁基吡啶鎓氯化物。
23.根据权利要求14的方法，其中所述混合在室温或更低的温度下进行。
24.根据权利要求23的方法，其中所述混合在20℃或更低的温度下进行。
25.根据权利要求14的方法，其中所述仲醇是异丙醇。
26.根据权利要求14的方法，其中所述离子液体是催化剂。
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