CN100431946C - 生产金属氧化物的方法及所述方法生产的金属氧化物和用途 - Google Patents

生产金属氧化物的方法及所述方法生产的金属氧化物和用途 Download PDF

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CN100431946C
CN100431946C CNB038266679A CN03826667A CN100431946C CN 100431946 C CN100431946 C CN 100431946C CN B038266679 A CNB038266679 A CN B038266679A CN 03826667 A CN03826667 A CN 03826667A CN 100431946 C CN100431946 C CN 100431946C
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metal
oxide
metal oxide
cerium
carboxylate
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CN1787964A (zh
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J·W·斯塔克
S·E·普拉特斯尼司
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Abstract

公开了一种生产纯或混合金属氧化物的方法，其中至少一种金属前体被形成为液滴并例如被火焰氧化，所述金属前体是每一羧酸基团的平均碳值至少为3的金属羧酸盐，例如2-乙基己酸盐。在液滴形成之前，在通常为小于40mPas的粘度下进行该方法，所述粘度可通过加热和/或通过添加一种或多种焓值充分高的低粘度溶剂而获得。

Description

生产金属氧化物的方法及所述方法生产的金属氧化物和用途
技术领域
本发明涉及金属氧化物的特殊类型的制造方法和通过所述方法获得的具有特殊特征的金属氧化物，尤其铈、锆、钆、铁、锰的氧化物、混合氧化物，尤其碱土金属钛酸盐、碱金属锰酸盐、稳定的氧化锆和二氧化铈。
背景技术
金属氧化物，尤其混合金属氧化物具有宽范围的应用，例如陶瓷、聚合物添加剂、填料、颜料、反应性表面、催化剂、存储材料、抛光添加剂、膜、燃料电池等。最重要的金属氧化物是二氧化铈，铈-锆和其它稳定的氧化锆混合氧化物，钛酸盐和以下称为陶瓷氧化物的其它混合氧化物。若这些材料用作纳米颗粒(粒径低于200nm)，则它们显示出有利的性能，例如高的催化活性、改进的加工能力、低的烧结温度、良好的分散能力，此处仅仅列举了一些。钛酸盐用作电容器的电介质。由于降低的尺寸特征要求较薄的电介质片材和由于这种较薄的片材优选由非常小的颗粒，例如纳米颗粒制造，因此纳米颗粒是高度令人感兴趣的。
目前生产金属氧化物的方法是机械和机械/热方法、湿相(wet-phase)化学基方法和高温法，例如火焰喷涂热解(FSP)。对于后者来说，驱动转化成纳米尺寸氧化物的能量可以是射频(等离子体)、微波、激光或冲击波。然而，最方便的是使用热能，因为在大多数情况下，这是最便宜的能源。
机械和机械/热方法(研磨)耗能大，且通常具有在原子水平下混合不充分的缺点，从而导致低的相稳定性和/或低的比表面积。来自研磨(磨耗)的杂质会降低产品纯度和性能。
湿相基方法使得需要大的溶剂成本，产生大量废水并需要在合成之后的焙烧步骤，从而使得它们成本大。此外，尽管例如二氧化铈/氧化锆的共沉淀可导致极高比表面积的混合氧化物粉末，但遗憾的是，如此制备的氧化物的温度稳定性的特征在于在升高的温度下比表面积的较大损失。对于大多数湿相制造的陶瓷来说，观察到相同的结果。在高温下制备可产生具有增加稳定性的氧化物。这促使人们尝试通过火焰喷涂基方法制备氧化物。火焰喷涂热解(FSP)是一种已知的方法且用于制备许多氧化物。它利用热能且具有采用低的能量成本驱动形成纳米颗粒的固有优点。然而，在许多氢氧化物的情况下，对合适的前体的研究必然引起与这些化合物化学性能有关的巨大问题。例如，Yoshioka等(1992)利用FSP生产铈的氧化物，但他们得到低比表面积的粉末。WO 01/36332公开了一种FSP方法，其导致含宽范围变化尺寸的二氧化铈颗粒的不均匀产品。Aruna等(1998)研究了通过燃烧氧化还原化合物的混合物并氧化金属前体合成二氧化铈/氧化锆。这一高温制备在如此制备的粉末内得到具有明显良好的相混合的高表面积产品。然而，通过固体燃烧制备陶瓷难以高生产速度地实现，这是因为该方法可快速失控。此外，它基本上是一种间歇方法，和重现性是一个常见的问题。Laine(1999)和Laine等(2000)使用喷涂热解装置制备陶瓷氧化物，但产品粉末的比表面积仍然保持较低，为10-16m2/g。EP1142830还公开了由有机金属化合物为起始，在有机溶剂和/或水中制备二氧化铈/氧化锆的FSP方法。在EP1142830中公开的步骤集中在通过火焰喷涂热解生产的无氯粉末上，并使用MeR类型的前体溶液，其中R是有机部分，如甲基、乙基或相应的烷氧基部分或硝酸根阴离子。作为溶剂，使用水或醇，US 5997956公开了其中在接近其临界温度下，液体或液体状流体被注射到火焰或等离子体火炬内，进而转化成纳米颗粒的方法。
WO 02/061163A2公开了生产粉末或膜涂层的装置。于是，在没有使用分散气体的情况下雾化含金属的液体。Oljaca等(2002)公开了使用类似的喷嘴制造纳米颗粒的方法。他们仅仅描述了在以金属计小于0.05M的溶液的情况下的非常低的生产速度。液滴尺寸分布被描述作为成功的纳米颗粒合成的主要参数。他们尤其报道了氧化钇稳定的氧化锆的合成。
最近，
Figure C0382666700081
等(2002B)公开了使用两相喷嘴，通过分散气体(氧气或空气)分散含液体的金属，并通过围绕所述喷嘴周围的预混火焰(falame)使所得喷雾点火，生产具有高表面和均匀粒度的纯二氧化铈的FSP方法。此外，在该文献中，这种燃烧器被称为喷雾燃烧器。然而，现已发现，
Figure C0382666700082
等所使用的溶剂体系不适合于生产例如二氧化铈/氧化锆。Stark等(2003)公开了使用乙酸和月桂酸制备二氧化铈、氧化锆和二氧化铈/氧化锆。Maric等(2003)使用没有进一步鉴定的CxH2zCeO6前体制备用于燃料电池膜的二氧化铈、氧化钆和氧化钐掺杂的二氧化铈。他们采用在低的生产速度下操作并使用制造非常小液滴(低于10mm)的Nanomiser装置(WO02/061163A2，参见上面)的不含分散气体的雾化装置。甚至使用这种多喷嘴设备时，总的生产速度仍然低于1kg/h。
为了使纳米颗粒的制造从中试规模生产变为工业规模合成(千克变为吨的数量)，要面对一些额外的问题。最突出的是选择可容易获得的金属前体，所述金属前体使得可提供高的生产速度。本发明将纳米颗粒的制造与为不同的应用而开发但不是制造纳米颗粒的已有的含金属产品相关联。第二个问题是生产速度。如WO02/061163A2中一样使用多排必然会产生维护、喷嘴堵塞、空间、重现性和其它问题。非常优选的是使用较少的燃烧器制造相同量的粉末。进一步非常有用的是采用可在大多数常规的燃油器上喷雾但不要求复杂雾化设备的金属载体液体，如WO02/061163中一样。这进一步非常有助于进一步扩大规模生产，因为可获得远高于100kg油/h的燃油器。在本发明内，显而易见的是，这种燃烧器可实现最多20kg陶瓷颗粒/h(对于100kg的进料/h来说)。
对于例如二氧化铈、氧化锆和二氧化铈/氧化锆来说，迄今为止所有的已知方法使用得到低生产速度的稀释金属溶液(通常＜0.15mol金属/L)。高金属浓度是有利的，因为它们直接增加该方法的生产速度。因此，在载体液体内的金属浓度应当尽可能高。在本发明的范围内，发现火焰喷涂方法因粘度导致限制可能的载体液体配方的范围，因为液体必须在该工艺过程中分散。尽管发现液滴尺寸不那么重要，但非常粘稠的液体根本不可能喷雾。因此，高度感兴趣的是寻找用于火焰喷涂合成的氧化物和金属纳米颗粒的前体，其兼有低粘度和高的金属浓度。此外，这种配方应当容易生产且在储存时稳定。本发明再一目的表明，若金属载体液体显示出以上所述的特征，则可使用常见的燃油器用于纳米颗粒的合成。
发明公开
因此，本发明的一般目的是提供适合于生产具有改进特征和因此具有宽范围应用的金属氧化物的方法以及提供这种金属氧化物。
本发明另一目的是具有高均匀度且以高生产速度生产的二氧化铈、氧化锆、稳定的氧化锆、铁或锰的氧化物、锰酸锂或钛酸钙和钛酸钡的纳米粉末。
本发明再一目的是本发明的金属氧化物作为催化活性体系的至少一部分，尤其内燃机用的催化活性体系的至少一部分，或者机械化学抛光，或者在磁铁、电子组件、机械传导装置中，作为压电或储能元件的用途。
本发明另一目的是通过添加另一金属氧化物，如二氧化铈、氧化钆或氧化钇稳定氧化锆，以用于燃料电池、传感器中和作为结构陶瓷或用于涂料中。
本发明再一目的表明，若采用特殊质量的含金属的液体，则普通的燃油器可用于纳米颗粒的合成。
本发明另一目的是，工业金属配方非常适于纳米颗粒合成。尽管杂质降低热稳定性，但对于其中杂质不那么重要的高容量(high-volume)应用来说，这种颗粒仍高度令人感兴趣。这种应用可在陶瓷中作为遮光剂(低等级的氧化锆)。
为了实施本发明的这些和进一步的目的(根据下述说明，这些将变得显而易见)，通过下述特征来显示本发明的金属氧化物，这些特征可通过本发明的方法获得。
生产本发明金属氧化物的方法的特征在于，将至少一种金属羧酸盐(羧酸与金属的盐)溶解在含最多40％羧酸或羧酸混合物的高焓(通常＞25kJ/g)溶剂内，形成溶液，和其中所述溶液然后形成为液滴并藉助高温方法转化成纳米颗粒。这种金属羧酸盐(也称为金属皂)通常大量地在树脂、漆内用作催干剂，在聚合物制造中用作添加剂，用作燃料添加剂和在薄膜的制造中使用。一些还发现可用作金属源用于动物皮肤的防腐。因此，这种金属皂可容易获得、稳定且可容易加工，或者可通过任选地但通常优选地在较高的温度下，用合适的酸处理金属前体，来获得金属皂。合适的金属皂是具有可容易替换的阴离子的那些。优选的阴离子是呈质子化形式可容易除去，以便没有建立任何平衡和反应进行到几乎100％的那些，例如氧化物、氢氧化物、碳酸盐、卤化物，例如氯化物和溴化物，和低级醇盐。
纯的(这些金属皂中的许多具有低的熔点，以便在升高的温度下，他们具有充分低的粘度)或者溶解在额外的溶剂内的这种金属皂是制造纳米颗粒的高度合适的前体。其部分最有利的用途是可利用高的生产速度的事实(以溶解形式存在，大于100g二氧化铈/升载体液体，或者超过200g氧化锆/升载体液体)，而这在常规的制备方法中成为主要的问题。在常规的制备方法中，金属的溶解度或高粘度(难以喷雾)将生产速度限制到较低的数值(
Figure C0382666700101
等，2002实现26g二氧化铈/升前体液体)。Oljaca等(2002)使用小于0.05M的溶液(对应于8.6g二氧化铈或6g氧化锆/h)，而根据本发明，可制造高于1M的溶液。
现已发现，在FSP中使用在本发明范围内公开的前体混合物使得可高生产速度地生产纯氧化物和混合氧化物，如二氧化铈、氧化锆、氧化钆、钛酸盐、锰酸盐和稳定的氧化锆，同时保持在原子水平下的良好混合、优良的比表面积(例如良好的可接近性)和高的相稳定性的有益性能。
对于FSP来说，前体或前体混合物分别需要将充足的金属携带到高温区或优选火焰内，在高温区或火焰内分配所述金属，并支持稳定的燃烧或转化和喷雾工艺。在许多金属，例如铈的情况下，这必然伴有下述问题：
-很少有机金属化合物是已知的，所有有机金属化合物相当昂贵和/或含有其它非所需的元素，如卤素。
-便宜的前体主要是水溶性前体。然而，水对于FSP来说是非常差的主要成分，因为为了实现所需的高温，它成本高和设备花销大(等离子体、激光、微波、高度稀释)。
此处公开的方法避免了这些问题。
附图简述
当考虑下述详细说明时，可更好地理解本发明，和以上列出的目的以外的那些目的将变得显而易见。这些说明参考附图，其中：
图1示出了摘除导引管的常规燃油器(分散喷嘴)的顶视图。中间由2相喷嘴组成，其中油或在此情况下，含金属的液体在所述2相喷嘴内分散。截面通道传输空气以支持燃烧。
图2示出了以540g/h生产氧化钙稳定的氧化锆纳米颗粒的常规燃油器。
图3示出了由0.4M的Ce和Zr的溶液(各自为0.4M)制备的二氧化铈/氧化锆(CeZrO4)的透射电子显微镜图像。左侧是通过使用118g/l的载体液体的生产速度制备的二氧化铈/氧化锆Ce0.5Zr0.5O2的透射电子显微镜(TEM)照片。在右侧是在700℃下在空气中热处理16小时之后的二氧化铈/氧化锆Ce0.5Zr0.5O2的透射电子显微镜(TEM)照片，这表明这种热处理导致类似形状的较大颗粒。
图4示出了由0.4M的Ce和Zr的溶液制备的CeZrO4的X-射线衍射光谱(XRD)图。
图5示出了如此制备的氧化钆掺杂的二氧化铈(Gd0.1Ce0.9O1.95；氧化钆/二氧化铈)的X-射线衍射光谱(XRD)。它描述了非常小晶体的宽信号并证实两种金属的优良混合程度和尖锐的峰强调混合氧化物的相稳定性。它示出了为了形成纯的混合氧化物相，在火焰中可如何极其均匀地传输不同的氧化物。
图6描述了由环烷酸锰制备的氧化锰纳米颗粒的XRD图。
图7是由溶解在2-乙基己酸内并采用二甲苯作为溶剂的钡和钛的前体制备的BaTiO3的XRD图。
图8是辛酸钙以及由四异丙醇钛和2-乙基己酸制备的辛酸钛得到的钛酸钙的XRD图，从而表明可由将转化成金属皂的含钙和钛的前体获得钛酸钙。下部的曲线给出了如此制备的XRD和上部的曲线给出了在600℃下在空气中烧结2小时之后的氧化物。在图9中示出了产品的TEM图像。
图9给出了按照实验工序如此制备的电子材料的TEM图像。左侧：在电池储能材料中使用的LiMn2O4颗粒，右边：在电介质或其它应用中使用的CaTiO3。在这两种材料中，观察到相当均匀的粒度，从而表明在整个反应器中形成均匀的颗粒。
图10是由相应的辛酸钆在二甲苯/2-乙基己酸(10∶1体积比)中制备的氧化钆的XRD图。
图11给出了氧化锂锰的XRD图。如此制备的粉末主要由黑锰矿和一些无定形部分组成。加热到400℃对于形成混合氧化物尖晶石相来说是足够的。
实施本发明的模式
本发明的金属氧化物可通过下述方法获得，其中使用纯或溶解形式的至少一种金属羧酸盐(“金属皂”)，和其中所述液体然后形成为液滴并在高温环境内，尤其在火焰内氧化。
本发明使用金属羧酸盐(金属与一种或数种羧酸的盐)作为金属源以供高温转化，尤其火焰喷涂合成纳米颗粒氧化物，金属皂以纯或溶解在额外溶剂内的形式使用，以实现合适的粘度。
在本发明方法的较优选的实施方案中，前体液体基本上由纯或溶解在溶剂内的一种或数种金属皂(存在工业溶剂的常见杂质是可接受的)组成。任选地，可在喷涂之前加热这些前体。该液体的特征在于，对于一些金属来说，至少13kJ/g的净燃烧热，优选地，和更通常采用至少18kJ/g，更优选至少22.5kJ/g，最优选至少25.5kJ/g，和粘度小于100mPas，优选小于50mPas，最优选小于20mPas。这通过使用纯金属皂(任选地加热到使其粘度下降的升高的温度下)或者通过在额外的溶剂内溶解金属皂，使之具有合适的粘度和燃烧能来实现。
为了降低前体的粘度，常常有利地使用烃如甲苯、二甲苯、己烷或轻质石蜡油和金属羧酸盐的混合物，其中相应的羧酸具有的平均碳数至少为3个/个羧酸基团以确保低粘度、充足的溶解度和燃烧能。优选的溶剂混合物包括具有的平均碳数至少为4个，更优选至少5个，尤其5-8个/个羧酸基团的金属皂，其中羧酸通常具有不大于30C和优选选自一个或多个C3-C18单羧酸，更优选一个或多个C4-C12羧酸，和最优选一个或多个C5-C8羧酸。即使可使用大于8的平均碳含量，但这样较高的平均碳含量通常降低生产速度。
同样合适的是螯合酸，例如二羧酸，多羧酸，氨基羧酸，羟基羧酸，条件是它们提供充足的焓或者与任选地存在的溶剂相容，以降低粘度/或提高焓。合适的羧酸包括直链或支链酸，所述酸可以是饱和或者不饱和酸，和任选地进一步被取代，只要该取代基没有过度地影响酸的高焓或者金属皂的熔点或溶解度即可，其中所述酸的焓优选为至少13kJ/g，更优选至少18kJ/g，较优选至少22.5kJ/g，和最优选至少25.5kJ/g。对于许多重金属氧化物来说，2-乙基己酸的金属皂显示出所需的性能且非常适合于火焰喷涂合成。在其它情况下，例如生产钛酸盐的情况下，金属皂可直接就地由含金属的前体通过与羧酸反应而制造。这种溶液可与另一金属皂混合并容易地产生金属氧化物，例如钛酸盐，如钛酸钙和钛酸钡。如上所述，合适的金属前体尤其是具有可通过例如加热，任选地在真空下容易地除去的阴离子的呈质子化形式的那些金属前体。
如前所述，除了未取代的单羧酸的金属皂以外，可采用其它的金属羧酸盐直到观察到某些局限。在此情况下，可有利地或者甚至需要将酸以通常最多40％的用量加入到溶剂内。取决于由一种或多种酸衍生的金属皂的阴离子，用作溶剂的一种或多种酸可以是直链或支链、饱和或不饱和、未取代或取代的单羧酸，条件是它们导致合适的高焓溶剂。这种酸包括具有极性取代基如-OH、-NH2或-CONH2基的酸，这种酸可用于调节溶剂到特定的需要。在特定情况下，也可使用足够长链的任选取代的饱和或不饱和二羧酸或多羧酸。
然而，在许多情况下，不需要酸或者甚至酸是不利的。已发现，具有高的平均碳含量的金属羧酸盐，尤其具有至少C4单羧酸的盐，优选至少C5单羧酸的盐，容易溶解在低分子量和/或低粘度的非极性溶剂，如甲苯、二甲苯、低级烷烃如己烷、石油溶剂内，但也可是轻质石蜡油、醚等内。
目前优选的金属皂是具有未取代、直链或支链、饱和或不饱和单羧酸的那些金属皂，例如2-乙基己酸，和优选的溶剂是至少60％，优选至少80％，较优选几乎100％非极性溶剂，尤其选自甲苯、二甲苯、低级或低粘度烷烃，例如己烷、异辛烷、低级或低粘度烯烃、低级或低粘度炔烃或其混合物中的溶剂。
在本发明的又一突出方面中，可通过在升高的温度下，用相应的一种或多种羧酸，处理前体，例如氧化物、氢氧化物、卤化物、碳酸盐或醇盐，通过就地形成金属皂，最终通过添加额外的溶剂来降低粘度，和氧化，尤其火焰喷涂所得的混合物，将氧化物转化成纳米颗粒。所得氧化物由粒度分布非常窄的纳米颗粒制成。图表1示出了该工艺的概况。
图表1将氧化物转化成相应的纳米颗粒的羧基方法
  工序   实施例
  氧化物   氧化钆(99％)
  制造金属皂   66.6g Gd<sub>2</sub>O<sub>3</sub>，200ml 2-乙基己酸，35ml乙酸酐，在140℃下回流10h，除去一些乙酸
  调节粘度   用二甲苯稀释金属皂
  火焰喷涂   如实验部分所报道的在甲烷/氧气火焰中喷雾
  收集纳米颗粒   具有70m<sup>2</sup>/g表面积的Gd<sub>2</sub>O<sub>3</sub>纳米颗粒
在本发明的方法中，火焰或高温区的温度为至少600℃，通常至少1200℃，优选至少约1600℃。对于许多应用来说，火焰温度的优选范围为1200-2600℃。
液滴的平均直径可随液体分散设备和液体本身的性能而变化。一般来说，平均液滴直径范围为0.1微米-100微米，优选1微米-20微米。若采用此处公开的前体溶液，则液滴直径不那么重要。这是非常有利的，因为它便于使用最常规的可商购的燃油器将此处所述的液体转化成相应的氧化物。仅仅作为例举，合适的燃油器以牌号OEN-151LEV或OEN-143LEV或OEN-331LZ到OEN-334LZ获自Vescal AG，Heizsysteme，Industriestrasse 461，CH-4703Kestenholz。
优选地，进行热氧化的液滴包括浓度至少0.15mol/L的金属。这一浓度导致至少0.15mol金属或金属氧化物/个喷嘴的生产速度。
若为了充分转化，使用具有不足氧气的火焰，进行本发明的方法，则这种氧气的缺少会导致形成亚化学计量的氧化物或金属及其混合物，其也具有用途。
此外，通过在氧化之后添加进一步的步骤，如此生产的金属氧化物可藉助额外的处理，例如用氨、氢气等处理，转化成相应的非氧化物，如氮化物、硼化物、碳化物。
本发明的方法可用于生产宽范围的金属氧化物，尤其混合金属氧化物。可使用特定的羧酸作为溶剂，通过本发明的方法制备的进一步的氧化物体系例如是，纯过渡金属氧化物和混合碱金属或碱土金属和过渡金属氧化物，如碱金属锰酸盐，特别是锰酸锂或钴酸锂，或钙、锶、钡的钛酸盐或锆酸盐及其混合物，但也可以是其它氧化物，例如铁或锰的氧化物。
这种氧化物，尤其若由纯前体制备的氧化物，具有高的热稳定性，其特征在于，在600℃下烧结1小时之后，比表面积(BET)为至少20m2/g。
与无杂质的纯的混合金属氧化物相反，可生产具有杂质和与迄今为止已知的氧化物相比，具有优异特征的氧化物，在高温氧化之后，其比表面积(BET)通常为至少5m2/g，优选至少10m2/g，尤其至少15m2/g。提供这一表面积的杂质例如是碱金属、碱土金属、过渡金属或稀土金属，但也可以是氯化物、氟化物或溴化物、磷酸盐、硫酸盐或硅和主族金属，如Al、B等，其含量范围为0.5-5wt％，尤其0.8-5wt％。
可通过本发明的方法获得的优选金属氧化物的特征在于，质均初级粒度分布小于2或者直径大于500nm且比表面积大于3m2/g的固体初级颗粒小于2wt％的几何标准偏差。这种金属氧化物颗粒适合于粉末注塑或者光学透镜抛光。
较优选的金属氧化物是用铈和/或钇，优选铈或钇，尤其用量为最多20％的铈和/或钇稳定的氧化锆。
可获得具有特定性能的一般的二氧化铈基氧化物和一般的氧化锆基氧化物，以及LiNbO3、BaTiO3、SrTiO3、CaTiO3、LiyMnOx和衍生物、NiO、LixTiOy、用于医疗植入物的磷灰石、金属掺杂的氧化钛、稀土金属氧化物，特别是镧基钙钛矿，含土金属和过渡金属族中的元素的混合氧化物，含碱金属和过渡金属中的元素的混合氧化物、铝酸盐、硼酸盐、硅酸盐、磷酸盐、氧化铪、氧化钍、氧化铀等。在实验部分中给出了一系列代表性实例。
本发明的方法还包括由与其它前体，尤其有机金属或有机准金属前体相结合的金属皂生产金属氧化物，条件是溶解度和焓保持在此处列出的范围内。可对如此制备的氧化物直接进行后处理，为的是形成氮化物、碳化物、硅化物、硼化物和其它。
生产纯或混合金属氧化物的合适金属例如是铈、锆、任何稀土金属、锂、钠、钾、铷或铯、镁、钙、锶、钡、铝、硼、镓、铟、锡、铅、锑、铋、钪、钇、镧、钛、铪、钒、铌、钽、铬、钼、钨、锰、铼、铁、钌、锇、钴、铑、铱、镍、钯、铂、铜、银、金、锌、镉、钍、铀或硅，其中优选的混合金属氧化物是铈与稀土元素或锆和/或氧化铝，锆与钇、钪、铝或碱土金属，钛和碱金属或碱土金属，锰、钴、镍和铁并结合锂或另一碱金属，锂和铌、钨或钼，钡与铝和铂，铝与铂或钯，铜和铝或锆和锌，铅和碱金属或碱土金属，锡和铂，铟和锡或锌，镧和铁、锰、钴或镍，镁和铝。
许多便宜的基本上纯的金属氯化物是可商购的。因此，本发明的优点是，不含水的金属氯化物的混合物可用作金属源。所述混合物然后与羧酸反应，通过脱气和/或加热所得溶液除去所形成的氯化氢。然后，这种溶液可用于制造氯化物含量小于0.1wt％的氧化物。
本发明的金属氧化物，尤其混合金属氧化物，具有本身已知的应用且由于其改进的性能导致具有拓宽的应用领域。
本发明的金属氧化物，例如二氧化铈、氧化锆或二氧化铈/氧化锆，由于其良好的均匀度，因此可用于化学机械抛光，条件是它们具有高的纯度。
考虑到均匀的颗粒结构，本发明的氧化物因此适合于在结构陶瓷中制造涂层，或者用于保护在金属上的保护层。
本发明的金属氧化物一般来说可用作至少一部分的催化活性体系，尤其用于内燃机的催化活性体系，和/或用于化学机械抛光，和/或在固体氧化物燃料电池中，和/或在电池中或者在可充电电池中，特别是在Li离子电池中用作电解质或膜，和/或用于至少一种下述目的：作为非均相催化剂，作为NOx储存催化剂，作为润滑剂，作为结构陶瓷，作为电池储能材料，用于化学传感器，用于能量生产的元件，用于太阳能生产元件，在可循环电池装置中用于储电，作为电介质，作为压电体、用于微型传导装置中，用作铁电体，用作透气膜，用作颜料，聚合物添加剂，稳定剂，磁性流体，抛光粉末，用于金属合金内的添加剂，在铠装层的制造中，在微电子中，作为电极原料，用作磷光体用于辐射敏感元件和显示器中，用于激光器、化妆品、药物包装中，在食品和药物应用中的添加剂，燃料电池和/或超导体。
通过本发明获得的具有整体结构的二氧化铈，和/或优选二氧化铈/氧化锆的一种优选应用是作为催化剂。对于这种催化剂，二氧化铈和/或二氧化铈/氧化锆可与得到整体结构的材料，例如Al2O3混合。二氧化铈和/或二氧化铈/氧化锆可以是覆盖整体结构载体的层。
此外，这种催化剂可包括额外的催化活性物质，例如进一步的金属氧化物，例如氧化钛、氧化钒、氧化铬、锰、铁、钴、镍、铜的氧化物、和/或贵金属，例如铂、钯、铑、钌、铼、铱，其中所有这些单独地或以与其中的一种或多种的混合物或其合金的形式存在。优选的催化剂是铂/二氧化铈/氧化锆。
实施例
通用工序
通过在实验室规模的装置[
Figure C0382666700181
等，(2002A)，图1]或中试规模的燃油器(SYSTHERM，CH-8105Regensdorf，Typ NS1，Ausführung1.1，1988，Nr.20940；对照装置(Satronic Type ZT 801和MMD 870；Flicker检测器(Satronic IRP 1010)；燃烧器管长：0.23m，直径0.0825m；720L空气/h作为分散气体，3升液体/h，图1和2)中，通过火焰喷涂热解生产混合氧化物粉末。以下描述了标准的制备(随后表示为(3/3))。使含液体的金属通过注射泵(Inotech IR-232)以3ml/min进入火焰内。火焰由中心喷雾传输装置、预混的环形支持火焰(直径6mm，狭缝宽度150微米)和环形片状气体传输装置(烧结金属环，内径11mm，外径18mm，5升氧气/min)组成。在所有实验中，氧气(Pan Gas，99.8％)用作分散气体并以3升/分钟传输。甲烷(1.51/min，Pan Gas，99％)和氧气(3.2L/min)的混合物被供入到内部狭缝内，并形成预混火焰。通过校正的质量流控制器(Bronkhorst EL-Flow F210)控制所有的气体流速。
含金属的前体的制备
将相应量的金属皂溶解在二甲苯、甲苯、石油、轻质石蜡油或其它合适的溶剂内。任选地添加一些羧酸。以下给出了一系列的具有特定物质的制备方法。
铁或锰的氧化物纳米颗粒的生产
氧化铁
混合10ml环烷酸铁(Strem Chemicals，CAS no.[1338-14-3]、LOT no.138222-S，80％在溶剂油(mineral spirit)内，12wt％铁)与10ml二甲苯，从而导致暗红色的溶液。在甲烷/氧气喷涂火焰内以3ml/min喷雾这一前体(如同在二氧化铈/氧化锆实验中一样的实验参数)导致BET比表面积为71m2/g的氧化铁纳米颗粒。生产速度：85g氧化铁/升前体溶液。
氧化锰
混合10ml环烷酸锰(Strem Chemicals，CAS no.[1336-93-2]、LOT no.124623-S，56％在溶剂油内，6.0wt％锰)与10ml二甲苯，并在与对氧化铁来说相同的条件下火焰喷涂。相应的比表面积为80m2/g，和X-射线衍射证实形成Mn3O4作为主要组分。生产速度：42g氧化锰/升前体溶液。
锰酸锂尖晶石
按照(3/3)，在氧气/甲烷火焰内，喷雾0.75M环烷酸锰和0.375M的辛酸锂溶液。产物在400℃下在空气中保持1小时。XRD证实形成比表面积为91m2/g的尖晶石相。通过TEM证实窄的粒度分布(参见图9)。
钛酸钙
混合20ml 1.24M辛酸钙溶液(在石油溶剂/2-乙基己酸内)和7.4ml四异丙醇钛。当异丙醇被较强的酸性基团取代时，温热该溶液。然后用2体积的二甲苯稀释该溶液，并按照(3/3)喷雾，从而导致白色粉末。XRD证实形成比表面积为60m2/g的钛酸钙(参见图8)。在600℃下在空气中焙烧1小时导致45m2/g。
钛酸钡
混合10ml 0.5M辛酸钡溶液(2-乙基己酸/甲苯)和1.51ml钛。在冷却之后，添加5ml甲苯，降低粘度。按照(3/3)喷雾导致纯的白色粉末。原材料是非常无定形的，但在600℃下，在空气中保持1小时导致比表面积为36m2/g的纯钛酸钡相(XRD)。
氧化钙稳定的氧化锆的生产
实验室规模
使用标准参数，混合并喷雾3.5ml辛酸锆(IV)(工业级，SocTechSA，Bucharest，Rumania，CAS no.[18312-04-4]，16wt％锆)、8.5ml2-乙基己酸、5.5ml甲苯和0.5ml辛酸钙(工业级，SocTech SA，Bucharest，Rumania，CAS no.[242-197-8]，5.2wt％钙)。如此制备的粉末的比表面积为62m2/g，在空气中烧结(在700℃下16小时，以5℃/min升温)降低比表面积到19m2/g。
中试规模(最初的没有优化的试验)
在较大的燃烧器内以3kg/h喷雾2kg辛酸锆(IV)(工业级，SocTechSA，Bucharest，Rumania，CAS no.[18312-04-4]，16wt％锆)、0.66升轻质石蜡油和0.225升辛酸钙(工业级，SocTech SA，Bucharest，Rumania，CAS no.[242-197-8]，5.2wt％钙)(参见通用工序)的混合物得到白色、均匀的粉末，其比表面积为24.5m2/g。生产速度：187g/L前体。
二氧化铈和二氧化铈/氧化锆的生产
实验室规模
对于二氧化铈来说，用5.5ml甲苯和2ml 2-乙基己酸稀释10.5ml辛酸铈(III)(SocTech SA，Bucharest，Rumania，工业级，CASno.[56797-01-4]，10.2wt％铈，含有0.14wt％的Na)。使用标准参数喷雾导致67m2/g和在空气中烧结之后导致10m2/g的比表面积(在700℃下16小时，以5℃/min升温)。喷雾高等级前体导致高得多的稳定性，如结果部分所述。
中试规模(最初的没有优化的试验)
在较大的燃烧器内以3kg/h喷雾0.75kg辛酸铈(III)(SocTechSA，Bucharest，Rumania，工业级，CAS no.[56797-01-4]，10.2wt％铈，含有0.14wt％的Na)和0.275升轻质石蜡油(参见通用工序)的混合物得到浅黄色的比表面积为18m2/g的均匀粉末，在空气中烧结之后(在700℃下16小时，以5℃/min升温)比表面积为4m2/g。生产速度：90g/L前体。
实验室规模
对于二氧化铈/氧化锆来说，用4ml甲苯稀释10.5ml辛酸铈(III)(SocTech SA，Bucharest，Rumania，工业级，CAS no.[56797-01-4]，10.2wt％铈，含有0.14wt％的Na)和3.5ml辛酸锆(IV)(SocTech SA，Bucharest，Rumania，CAS no.[18312-04-4]，16wt％锆)。使用标准参数喷雾导致69m2/g和在空气中烧结之后导致28m2/g的比表面积(在700℃下16小时，以5℃/min升温)。甚至在使用这一工业质量的前体情况下，稳定效果是显然可见的。
中试规模(最初的没有优化的试验)
在较大的燃烧器内，以3kg/h喷雾2.5kg辛酸铈(III)(SocTech SA，Bucharest，Rumania，工业级，CAS no.[56797-01-4]，10.2wt％铈，含有0.14wt％的Na)、0.833kg辛酸锆(IV)(SocTech SA，Bucharest，Rumania，CAS no.[18312-04-4]，16wt％锆)和0.833升甲苯的混合物得到比表面积为21m2/g浅黄色的均匀粉末，在空气中烧结之后(在700℃下16小时，以5℃/min升温)比表面积为14m2/g。生产速度：125g/L前体。
结果与讨论
粘度的重要性
当在喷雾过程中金属载体液体分散成小液滴时，粘度必须足够低，以允许良好的液体分布。下表1示出了对于火焰喷涂合成来说液体粘度在哪一范围内是合适的。
表1
  金属载体液体   粘度/mPas   若在298K下，对火焰喷涂来说是否合适
  在石油溶剂内80％的环烷酸铁   ＞100   否
  用二甲苯稀释的Ditto(1∶1)   3   是
  在石油溶剂内的56％的环烷酸锰   16   是
  用二甲苯稀释的Ditto(1∶1)   1.7   是
  在2-乙基己酸/甲苯(5∶2体积)的内0.4M铈、0.4M锆   5   是
  在石油溶剂内辛酸锆(16wt％Zr)   ＞100   否
  用二甲苯稀释的Ditto(3∶1)   10   是
  用癸烷稀释的Ditto(3∶1)   19   是
  用二甲苯(3∶1)稀释的在石油溶剂内的辛酸铈(10.2wt％铈)   22   是
  用癸烷稀释的Ditto(3∶1)   ＞40   取决于燃烧器
备注：粘度在环境温度下在流变仪(Haake VT 550Rheometer，Fisons，Digitana AG，8810Horgen)内测量。
用其它溶剂稀释金属羧酸盐表明这些溶液的依数性能。对于铈和锆前体二者来说，二甲苯降低粘度约2倍，与癸烷一样好。
作为溶解的替代方案，或者另外，可提供加热金属羧酸盐或含金属羧酸盐的混合物/溶液，为的是进一步降低粘度到优选超过40mPas。
材料纯度对热稳定性来说的重要性
作为钠或氯形式的额外元素，金属羧酸盐的制造方法对最终产品的稳定性具有重要的影响，给出了高纯度的各种形式的前体(＞99％金属含量)和工业级(低于99％金属，含有氯化物和主要是钠)的比较。对于其中在工业前体内的钠增加其烧结速度的二氧化铈来说，在烧结之后大液滴的稳定性变得明显，采用纯辛酸铈和额外1wt％钠的交叉实验导致与工业级前体情况相类似的比表面积损失。结果见下表2。
表2：
  等级  如此制备的SSA[m<sup>2</sup>g<sup>-1</sup>]  烧结的SSA[m<sup>2</sup>g<sup>-1</sup>]   生产速度[gL<sup>-1</sup>]
 二氧化铈   99.8％   125   71   69
 二氧化铈   工业级   67   10   69
 二氧化铈，1wt％Na   -   24<sup>a</sup>   -
 氧化锆   ＞99％   105   45   50
 氧化锆   工业级   121   24   50
 二氧化铈/氧化锆   ＞99％   94   83   59
 二氧化铈/氧化锆   工业级   69   28   59
备注：工业级尤其含有钠和氯。
a用氢氧化钠(在最终陶瓷内1wt％的Na2O)浸渍纯的火焰制造的二氧化铈并进行烧结。
等级：仅仅基于金属的纯度。
可使用的材料范围
所给出的实施例表明可制备比表面积高于60m2/g同时维持大于40g/h的生产速度的单一过渡金属氧化物。这种材料在宽范围的产品和方法中具有应用。电子材料、电池、铁电体、永久磁铁、线圈和磁性流体仅仅是一些例举。
所给出的实施例进一步表明可结合碱金属或碱土金属与过渡金属氧化物，形成相应的混合氧化物。这种材料可形成尖晶石、钙钛矿和其它令人感兴趣的相。它们作为电介质、压电体、传动装置，在膜中，作为传感器，在电容器、超导体和其它中具有应用。一些用作催化剂，作为高温应用的陶瓷或结构元件。
材料的均匀度
锰酸锂、钛酸钙或二氧化铈/氧化锆的透射电子显微镜图像表明，可通过此处所述的方法获得窄的粒度范围的纳米颗粒。这进一步通过X-射线衍射图案(其显示出形成大的晶体)得到支持。此外，特定的比表面积支持TEM观察到的粒度范围。这一数据显然表明本发明可用于制造纳米颗粒。
结论
羧基方法提供生产纳米颗粒的可容易接近的方式。使用金属皂作为主要前体，可使用甚至常规的燃油器合成纳米颗粒。尤其已经制造了过渡金属氧化物，来自碱金属、碱土金属、稀土金属和过渡金属系列中的元素的混合氧化物的颗粒，从而表明本发明方法的多样性。这种金属皂基液体兼有处理、储存和混合相容性以及高的生产速度。能由1升前体液体生产超过200g纳米颗粒，同时对燃烧器的类型、分散气体体系或火焰的类型相当不敏感，使得对于火焰喷涂合成来说，与任何其它金属传输体系相比，这些前体非常有利。
可使用甚至工业前体，但因此导致低得多的热稳定性。通过将钠掺杂到纯二氧化铈前体内得到这一效果的证据(参见表2)。
尽管示出并描述了本发明目前优选的实施方案，但要清楚地理解，本发明不限于这些实施方案，而是在下述权利要求的范围内可以变化地得到体现与实践。
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Claims (26)

1.一种生产金属氧化物或混合金属氧化物的方法，
其中至少一种金属前体被形成为液滴并在高温环境下氧化；
其中所述金属前体是每一羧酸根基团的平均碳数至少为5的金属羧酸盐；
其中所述金属选自
●铈、钪、钇、镧、任何稀土金属，
●锂、钠、钾、铷、铯，
●镁、钙、锶、钡，
●钛、锆、铪，
●锰、铼，
●铁、钌、锇，
其中所述金属前体存在于溶液中，所述溶液包括至少0.15mol金属/L，并且，
其中金属羧酸盐在火焰内被氧化。
2.权利要求1的方法，其中金属羧酸盐在形成为液滴之前的粘度为最多100mPas。
3.权利要求2的方法，其中通过加热和/或通过提供至少一种金属羧酸盐与至少一种粘度降低溶剂的混合物，来获得该粘度，所述粘度降低溶剂选自甲苯、二甲苯、己烷、轻质石蜡油。
4.权利要求1的方法，其中混合金属氧化物是
●铈与锆，
●锆与碱土金属，
●钛和碱土金属，
●锰结合锂或另一碱金属。
5.权利要求1的方法，其中在喷雾燃烧器内进行火焰氧化。
6.权利要求1的方法，其中在至少600℃的温度下进行氧化。
7.权利要求1的方法，其中由金属氧化物或者金属低级烷基氧化物起始制备金属羧酸盐。
8.权利要求1的方法，其中金属羧酸盐或含金属羧酸盐的溶液的焓为至少13kJ/g。
9.权利要求1的方法，其中使用的金属羧酸盐为工业级。
10.权利要求5的方法，其中生产速度为至少0.15mol金属氧化物或混合金属氧化物/个喷雾燃烧器的喷嘴。
11.权利要求1的方法，其中为了充分转化，在具有不足氧气的火焰内生产金属氧化物，从而导致形成亚化学计量的金属氧化物或混合金属氧化物。
12.通过权利要求1-11任何一项的方法获得的具有高的热稳定性的纯过渡金属氧化物和混合碱金属或碱土金属和过渡金属氧化物，其特征在于，在600℃下烧结1小时之后的比表面积(BET)为至少20m2/g。
13.通过权利要求1-11任何一项的方法获得的纯或混合金属氧化物，其中具有范围为0.5-5wt％的杂质，并且其中所述氧化物的比表面积(BET)为至少5m2/g。
14.通过权利要求1-11任何一项的方法获得的金属氧化物，特征在于，其具有质均初级粒度分布小于2或者直径大于500nm和比表面积大于3m2/g的固体初级颗粒小于2wt％的几何标准偏差。
15.通过权利要求1的方法获得的金属氧化物在粉末注塑或在光学透镜抛光中的用途。
16.通过权利要求1-11任何一项的方法获得的金属氧化物，它是用铈和/或钇稳定的氧化锆，其中铈和/或钇的用量为最多20％。
17.通过权利要求1-11任何一项的方法获得或者权利要求13、14和16任何一项的金属氧化物的用途，用作至少一部分催化活性体系。
18.权利要求17的用途，其中催化活性体系是汽车废气催化剂，和其中该氧化物是任选地具有铂族金属的二氧化铈基氧化物。
19.通过权利要求1-11任何一项的方法获得或者权利要求13、14和16任何一项的金属氧化物用于化学机械抛光的用途，其中该金属氧化物具有至少99wt％的纯度。
20.通过权利要求1-11任何一项的方法获得或者权利要求13、14和16任何一项的金属氧化物的用途，在固体氧化物燃料电池中用作电解质或膜。
21.通过权利要求1-11任何一项的方法获得或者权利要求13、14和16任何一项的金属氧化物在电池或者在可充电电池中的用途。
22.通过权利要求1-11任何一项的方法获得或者权利要求13、14和16任何一项的金属氧化物的用途，其用于至少一种下述目的：作为非均相催化剂，作为NOx储存催化剂，作为润滑剂，作为结构陶瓷，作为电池储能材料，用于化学传感器，用于能量生产的元件，用于太阳能生产元件，在可循环电池装置中用于储电，作为电介质，作为压电体、用于微型传导装置中，用作铁电体，用作透气膜，用作颜料，聚合物添加剂，稳定剂，磁性流体，抛光粉末，在金属合金内的添加剂，用于铠装层的制造中，用于微电子中，作为电极原料，用作磷光体用于辐射敏感元件和显示器中，用于激光器、化妆品、药物包装中，在食品和药物应用中的添加剂，燃料电池和/或超导体。
23.一种催化剂，它包括通过权利要求1-11任何一项的方法获得或者权利要求12、13、14和16任何一项的二氧化铈，或二氧化铈/氧化锆，且具有整体结构。
24.权利要求23的催化剂，它包括与得到整体结构的材料混合的二氧化铈，或二氧化铈/氧化锆。
25.权利要求23的催化剂，它包括在覆盖整体结构载体的层中的二氧化铈，或二氧化铈/氧化锆。
26.权利要求23-25任何一项的催化剂，它包括额外的催化活性的物质，选自金属氧化物，和/或贵金属，其中所有这些单独地或以与其中的一种或多种的混合物或其合金的形式存在。
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