CN101553314A - 活性提高的离子液体催化剂 - Google Patents

活性提高的离子液体催化剂 Download PDF

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CN101553314A
CN101553314A CNA2006800512624A CN200680051262A CN101553314A CN 101553314 A CN101553314 A CN 101553314A CN A2006800512624 A CNA2006800512624 A CN A2006800512624A CN 200680051262 A CN200680051262 A CN 200680051262A CN 101553314 A CN101553314 A CN 101553314A
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S·埃洛马里
T·V·哈里斯
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Chevron USA Inc
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Abstract

公开了活性提高的酸性离子液体催化剂的生产方法，所述方法包括在反应区中使新鲜酸性离子液体催化剂、金属和布朗斯台德酸混合足以增加所述离子液体催化剂的活性的时间。也公开了活性提高的酸性离子液体催化剂的生产方法，所述方法包括以下步骤：在反应区内使新鲜离子液体催化剂、金属和HCl混合足以增加所述新鲜离子液体催化剂的活性的时间；从所述反应区移出反应产物并回收所述处理过的离子液体催化剂的至少一部分。

Description

活性提高的离子液体催化剂
发明领域
本发明涉及酸性离子液体催化剂，并更具体地涉及活性提高的酸性离子液体催化剂及其制备方法。
发明背景
离子液体是完全由离子组成的液体。所谓的“低温”离子液体通常是熔点低于100℃，甚至往往低于室温的有机盐。离子液体可适合于例如在烷基化反应和聚合反应以及在二聚、低聚、乙酰化、复分解和共聚反应中用作催化剂和用作溶剂。
一类离子液体是熔融盐组合物，它们在低温下被熔融，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 -、卤铝酸盐例如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吡啶鎓卤化物的熔融盐作为电解质的用途的其他专利是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以及其作为溶剂在催化反应中的用途。
美国专利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这些组分生成，所述组分包括(i)至少一种三卤化铝，(ii)至少一种选自碱金属卤化物、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反应中最普遍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他实例也可以在美国专利5,731,101；6,797,853和在美国专利申请出版物2004/0077914和2004/0133056中找到。
在各种商业和工业应用中，采用催化剂来提高化学反应速率。通常，希望能够提高催化剂活性，因为催化材料一般都很昂贵。类似地，处理催化剂的设备也增加成本。催化剂活性的任何改进都会降低这些成本。活性更高的催化剂会使该催化剂在失活并需要更换或再生之前能够使用得更久。较高的催化剂活性也会允许使用较低的反应温度，或以增加产品产率的方式来操作。
发明概述
本发明尤其提供了活性提高的酸性离子液体催化剂的生产方法，所述方法包括在反应区内使新制的酸性离子液体催化剂、金属和布朗斯台德酸混合足以增加所述离子液体催化剂的活性的时间。
在一个实施方案中，本发明提供了活性提高的酸性离子液体催化剂的生产方法，所述方法包括以下步骤：在反应区内使新鲜离子液体催化剂、金属和HCl混合足以增加所述新鲜离子液体催化剂的活性的时间，并回收处理过的离子液体催化剂的至少一部分。所述活化处理可以在中性烃(即正构链烷烃)的存在下进行，以辅助搅拌。在这种情况下，通过倾析或其它分离方法移出烃层，然后将所述催化剂与金属和生成的金属卤化物过滤分开，由此回收处理过的催化剂。
发明详述
本发明涉及催化活性提高的酸性离子液体基催化剂，也就是说，所述催化剂比相应的新制的或未处理的催化剂表现出更大的催化化学反应的活性。参考某些具体的离子液体催化剂和由其所催化的过程来描述和举例说明本发明，但这些描述并不打算限制本发明的范围。本领域技术人员基于本文所包括的教导、描述和实施例可将所描述的方法应用到其他催化剂和过程中。
新鲜或未处理的催化剂是这样的催化剂，它是由例如卤化铵盐和卤化铝的化合所产生的催化活性材料的直接合成的结果。它是实施基本合成步骤所产生的催化剂，所述基本合成步骤产生具有催化活性的材料。
本文使用的具体实施例涉及使用离子液体体系的烷基化方法，所述离子液体体系是与氯化铝混合的胺基的阳离子物种。在该体系中，为了获得适合于烷基化化学的合适酸度，通常通过混合物一摩尔份数的合适的氯化铵和两摩尔份数的氯化铝来将所述离子液体催化剂制成完全的酸强度。为所述烷基化方法而举例说明的催化剂是烷基吡啶鎓氯铝酸盐，例如1-丁基-吡啶鎓七氯铝酸盐。
1-丁基-吡啶鎓七氯铝酸盐
通常，强酸性离子液体对于烷基化反应例如异链烷烃烷基化反应是必需的。在这种情况下，在离子液体催化剂方案中，氯化铝，它是与布朗斯台德酸组合的强路易斯酸，是优选的催化剂组分。
金属铝与HCl反应生成氢气和AlCl3。通过将金属铝和HCl引入到新鲜氯铝酸盐离子液体催化剂中来原位生成氯化铝，氯化铝是所述氯铝酸盐离子液体中的酸性组分。如本文所示，与新制的催化剂相比，处理过的催化剂在乙烯与异戊烷的烷基化反应中表现出更好的活性。
根据本发明的方法的实施方案使用来自金属铝和盐酸间的反应的原位生成的三氯化铝来增加新制的氯铝酸盐离子液体催化剂的活性。使用金属铝和HCl将原位生成AlCl3，这通过增加AlCl3在离子液体中的浓度来增加离子液体催化剂的酸度和活性。不受任何理论约束，所述原位生成的三氯化铝可能有助于增加离子液体中活性氯铝酸盐物种例如Al2Cl7 -，Al3Cl10 -的浓度，因此，提高了该催化剂的总酸度和活性。用这种方法，处理过的催化剂比新制备的催化剂更有活性。
在根据本发明的方法中所使用的金属不限于铝。本方法可以用于任何路易斯酸离子液体，而金属与布朗斯台德酸反应会产生路易斯酸组分。例如，当路易斯酸组分是ZnCl2时，可以用金属锌和HCl。其金属卤化物可以用作路易斯酸的其他金属包括Fe、Cu、Ti、Sn、B、Ga和In等。当在催化方法中使用氯铝酸盐离子液体时，金属铝是所选的金属，以避免AlCl3以外的金属氯化物对离子液体催化剂造成污染。
根据本发明的方法并不限于使用HCl来与合适的金属发生反应以产生路易斯酸。也可以用其它布朗斯台德酸，但并不限于HI、HBr、HF、H2SO4、H3PO4。在氯铝酸盐离子液体的情况下，氢卤酸(HI、HCl、HBr、HF)是所选的酸。在氢卤酸中，优选盐酸以避免引入卤化物以外的共轭碱，和优选避免引入氯化物以外的共轭碱。
如以下实例所示，用铝和氯化氢来处理新鲜离子液体催化剂。将铝和氯化氢加入新鲜离子液体催化剂中，并在0-50℃和自生压力下搅拌所得到的混合液(在高压釜中)，生成比新鲜催化剂活性更高的催化剂。处理过的离子液体催化剂通过过滤从剩余的混合物(新制的AlCl3和金属铝)中移出。
通过用异戊烷来烷基化乙烯来测试所述回收的活化的离子液体催化剂的活性，和该催化剂表现出比处理前的新制催化剂更好的活性。处理过的催化剂的选择性与新制催化剂的选择性相同。
在本发明的一个实施方案中，将新鲜离子液体催化剂连续引入到搅拌釜反应器(CSTR)中，而金属铝粉末通过螺杆式进料器加入。铝保持在惰性气体(氮气或其他气体)下以防氧化。以合意的比例加入HCl气体以生成AlCl3。排出反应产物并与烃溶剂(例如己烷)混合。所述溶剂可以是C5-C15的正构烃和它们的混合物，优选C5-C8。然后在重力倾析器中分离该混合物，从中排出更重的离子液体相。通过过滤除去未反应的铝。回收该处理过的离子液体催化剂。
反应条件通常包括：在作为溶剂的正构烃中，温度为-20℃至200℃，压力为大气压-5000psig，优选大气压-500psig，接触时间为0.1分钟-24小时，优选为1/4-2小时。
根据本发明的方法可以作为酸性离子液体催化剂的完整制备部分来进行。它可以在同样的反应体系或在单独的反应体系中进行。
以下实施例是本发明的说明性的实施例，但是并不打算以任何超出含于所附的权利要求中的内容的方式限制本发明。
实施例
实施例1新鲜1-丁基吡啶鎓氯铝酸盐离子液体催化剂A(新鲜ILA)的制备
1-丁基吡啶鎓氯铝酸盐是室温离子液体，其通过在惰性气氛下混合纯净1-丁基吡啶鎓氯化物(固体)和纯净固体三氯化铝而制备。以下描述了丁基吡啶鎓氯化物和相应的1-丁基吡啶鎓氯铝酸盐的合成。在2L聚四氟乙烯内衬的高压釜内，使400g(5.05mol)无水吡啶(纯度99.9％，购于Aldrich)与650g(7mol)1-氯丁烷(纯度99.5％，购于Aldrich)混合。密封该纯净的混合物，让在125℃和自生压力下搅拌过夜。冷却高压釜并打开后，将反应混合物稀释并溶解在氯仿中，并转移至3L圆底烧瓶中。在旋转蒸发器里(在热水浴中)在减压下浓缩该反应混合物以除去过量的氯化物、未反应的吡啶和氯仿溶剂，得到棕色固体产物。在热丙酮中溶解所得的固体，并通过冷却和加入乙醚来沉淀出纯产物，由此进行产物的提纯。在真空下过滤并干燥，并在旋转蒸发器中加热，得到750g(产率88％)的作为白色发亮固体的预期产物。1H-NMR和13C-NMR与预期的1-丁基吡啶鎓氯化物一致，且没有观察到杂质。
根据下面的步骤，通过缓慢混合干燥的1-丁基吡啶鎓氯化物和无水三氯化铝(AlCl3)来制备1-丁基吡啶鎓氯铝酸盐。所述1-丁基吡啶鎓氯化物(如上述制备)在80℃下真空干燥48h以除去残留的水(1-丁基吡啶鎓氯化物是吸湿性的，且易于从接触的空气中吸收水)。将500克(2.91mol)干燥的1-丁基吡啶鎓氯化物在氮气气氛下转移至手套箱里的2L烧杯中。然后将777.4g(5.83mol)无水AlCl3粉末(99.99％，来自于Aldrich)分小批加入(搅拌中)以控制强放热反应的温度。一旦所有的AlCl3加完后，将所得到的琥珀状液体在手套箱中轻轻搅拌过夜。然后过滤该液体以除去任何未溶解的AlCl3。将所得到的酸性1-丁基吡啶鎓氯铝酸盐用作乙烯与异戊烷的烷基化反应的催化剂。
Figure A20068005126200091
实施例2用Al金属和HCl来活化IL A
根据下面的步骤，在间歇反应器中进行活化。在无氧气且无水的手套箱内，在300ml高压釜中，将如实施例1所述制备的75g新制的1-丁基吡啶鎓氯铝酸盐离子液体与8g铝粉末在氮气下混合。密封该高压釜，通过进口加入来自细压缩气瓶的5.5g无水HCl气体。在室温和自生压力(反应开始时230psig)下，用顶部搅拌器在约＞1200rpm下剧烈混合该混合物仅15分钟。反应温度升到约30℃，和压力降至203psig。打开高压釜(反应容器)并将其冷却回室温。然后，将该处理过的离子液体与铝粉末和产生的氯化铝过滤分开。由于离子液体相中存在过量的AlCl3，过滤后的离子液体在外观上有点呈乳状。使过滤后的催化剂沉降并再次过滤以得到外观上如新制催化剂一样澄清的处理过的(活化的)催化剂。根据实施例3所描述的步骤，通过用异戊烷来烷基化乙烯来测试该催化剂的活性。
实施例3使用异戊烷与乙烯的间歇烷基化反应来测定处理过的IL A的活性
异戊烷与乙烯的烷基化反应根据下面的步骤来进行。向300ml高压釜中装入42g离子液体催化剂、100g无水异戊烷、12g乙烯和0.3g无水HCl。然后以约1200rpm搅拌该反应并在自生压力下加热到50℃。起始压力通常为215-320psi。当压力降到个位数时，通常反应完成。反应结束时，打开反应器，并用GC检测气体样品的乙烯浓度。使液体反应混合物沉降成两相。倾析有机相并用GC分析来分析产物分布。下表1对新制催化剂与处理过的催化剂进行了对比。
表1
  新鲜催化剂   活化的催化剂
  反应时间   7分钟   3分钟
  起始压力   215psi   222psi
  结束压力   7   4
  iC5   69.1   67.7
  C7(总计)   19.1   20.3
  2，3-DM-戊烷   8.23   8.6
  2，4-DM-戊烷   10   9.7
  2，3-DM/2，4-DM   0.82   0.88
如表1所示，在金属铝上用HCl处理过的催化剂比新制的未处理的催化剂反应快得多。尽管两种催化剂产生相同的产物和选择性，但是根据其完成烷基化反应需要的时间更短看出处理过的催化剂更有活性。
根据本文所述的教导和支持性实施例，本发明有很多可变之处。因此，要理解的是，在所附的权利要求的范围内，本发明可以以与本文所具体描述的或举例说明的方式不同的方式加以实践。

Claims (24)

1.活性提高的酸性离子液体催化剂的生产方法，所述方法包括使新鲜酸性离子液体催化剂、金属和布朗斯台德酸混合足以增加所述离子液体催化剂的活性的时间。
2.权利要求1的方法，其中所述金属选自镁、铝、钛、镍、锌、铜、铁、镓、锡、铟、铜、锆、钒、铌、铬、钼和它们的混合物。
3.权利要求1的方法，其中所述布朗斯台德酸选自HI、HBr、HF、H2SO4、H3PO4和它们的混合物。
4.权利要求1的方法，其中所述金属为铝和所述布朗斯台德酸为HCl。
5.权利要求1的方法，其中所述离子液体催化剂被用来催化Friedel-Craft反应。
6.权利要求5的方法，其中所述Friedel-Craft反应是烷基化反应。
7.权利要求1的方法，其中所述条件包括使所述离子液体催化剂与足量的金属和过量的酸在-20℃至200℃的温度下和大气压-5000psig的下在作为溶剂的正构烃中接触0.1分钟-24小时。
8.权利要求7的方法，其中所述烃溶剂选自C5-C15的正构烃。
9.权利要求1的方法，其中所述离子液体催化剂包含咪唑鎓、吡啶鎓、磷鎓或四烷基铵衍生物或它们的混合物。
10.已经按照权利要求1的方法处理过的离子液体催化剂。
11.权利要求1的方法，其中所述离子液体催化剂是氯铝酸盐离子液体。
12.权利要求9的方法，其中所述离子液体催化剂是氯铝酸盐离子液体。
13.活性提高的酸性离子液体催化剂的生产方法，所述方法包括以下步骤：在反应区内使新鲜离子液体催化剂、金属和HCl混合足以增加所述新鲜离子液体催化剂的活性的时间；从所述反应区移出反应产物；将所移出的反应产物与烃溶剂混合；使所述混合物分成两相：较轻相和含有处理过的离子液体催化剂的较重相；并回收所述处理过的离子液体催化剂的至少一部分。
14.权利要求13的方法，其中所述金属选自镁、铝、钛、镍、锌、铜、铁、镓、锡、铟、铜、锆、钒、铌、铬、钼和它们的混合物。
15.权利要求13的方法，其中所述布朗斯台德酸选自HI、HBr、HF、H2SO4、H3PO4和它们的混合物。
16.权利要求13的方法，其中所述金属为铝和所述布朗斯台德酸为HCl。
17.权利要求13的方法，其中所述离子液体催化剂被用来催化Friedel-Craft反应。
18.权利要求13的方法，其中所述Friedel-Craft反应是烷基化反应。
19.权利要求13的方法，其中所述活化条件包括使所述离子液体催化剂与足量的金属和过量的酸在-20℃至200℃的温度下和大气压-5000psig的压力下在正构烃溶剂中接触0.1分钟-24小时。
20.权利要求13的方法，其中所述烃溶剂选自C5-C15的正构烃和它们的混合物。
21.权利要求13的方法，其中所述离子液体催化剂包含咪唑鎓、吡啶鎓、磷鎓或四烷基铵衍生物或它们的混合物。
22.权利要求13的方法，其中所述离子液体催化剂是氯铝酸盐离子液体。
23.权利要求21的方法，其中所述离子液体催化剂是氯铝酸盐离子液体。
24.按照权利要求13的方法制备的离子液体催化剂。
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