CN1127235A - 透氧混合导电膜 - Google Patents

透氧混合导电膜 Download PDF

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CN1127235A
CN1127235A CN95117797A CN95117797A CN1127235A CN 1127235 A CN1127235 A CN 1127235A CN 95117797 A CN95117797 A CN 95117797A CN 95117797 A CN95117797 A CN 95117797A CN 1127235 A CN1127235 A CN 1127235A
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oxygen
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T·J·马赞尼
T·L·凯博
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Abstract

本发明涉及新型的固态混合导电膜以及它们在高温下从含氧物料中分离氧的应用。该膜包括在空气中和25-950℃的温度下稳定的，基本是立方钙钛矿结构的，没有相连的贯穿孔的多成分金属氧化物，其中该膜是用下列通式表示的一种组合物：
[A1-xA′x][Co1-y-zByB′z]O3-δ，式中A≡Ca，Sr，Ba，和它们的混合物；A′≡La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；B≡Fe，Mn，Cr，V，Ti，和它们的混合物；B′≡Cu，Ni，和它们的混合物；～0.0001≤X≤～0.1；～0.002≤Y＜0.05；～0.0005≤Z≤～0.3；δ由金属价态决定。

Description

透氧混合导电膜
本发明涉及由混合导电氧化物形成的新型混合物导电膜以及使用该膜的方法。这一方法是在高温下从含氧物料中分离氧。该膜是氧离子和电子导体，它是形成基本上是立方钙钛矿结构的组合物，该结构在空气中和25-950℃的温度下基本上是稳定的。
申请人已发现稳定膜中立方钙钛矿相的组合物，而这些膜所具有的组合物以前在空气中和在室温大气压力至分离氧所用条件的范围内并不能维持立方钙钛矿相稳定。特别是，微量A位阳离子和微量B位阳离子能稳定ABCoO材料中基本上是立方钙钛矿的结构。另外，加入微量A位阳离子和B位阳离子在ABCoO材料中产生了立方钙钛矿相材料，而该ABCoO材料也会产生形成低氧流量的膜的立方相材料。
由氧离子导电材料形成的固态膜开始呈现出其用于从含氧流中分离氧的工业方法的前景。所展望的应用范围可以从医学上的小型氧泵到大量的气体生产和净化设备。该技术包括两种明显不同的膜材料，固体电解质和混合导体。由于混合导体传导氧离子和电子，并且在没有外部电路如电极，插头和电源的条件下就能操作，因此在从含氧物料中分离氧的方法中，由混合导体形成的膜比固体电解质优选。相反，固体电解质只传导电子，并需要外部电路以保持电子流动从而维持膜的离子化/去离子化过程。这样的电路增加了设备成本并使电解槽的几何结构复杂化。
当在典型的约500℃以上的温度下操作时，由固体电解质和混合导电氧化物形成的膜对氧有选择性并且能传送氧离子使之通过在固体晶格中动态形成的氧阴离子空位。固态电解质的例子包括用钇稳定的二氧化锆(YSZ)和氧化铋。混合导体的例子包括用钛掺杂的YSZ，用氧化镨改性的YSZ，并且更重要的是各种混合金属氧化物，这些混合金属氧化物中有些具有钙钛矿结构。
日本专利申请61-21717公开了由具有钙钛矿结构的多成分金属氧化物形成的膜，该钙钛矿结构由此式表达：
La1-xSrxCo1-yFeyO3-d，式中，x是0.1-1.0，y是0.05-1.0，d是0.5-0。
当在膜相对的两面存在氧分压差时，就可以利用在高温下操作由混合导电氧化物形成的膜而从含氧物料中选择性地分离氧。当氧分子离解成氧离子时就会发生氧迁移，氧离子迁移到氧分压低的膜一侧并在此处重新结合形成氧分子，而电子则以与氧离子相反的方向迁移过该膜以使电荷守恒。
氧透过膜的速率主要由三个因素控制。它们是(a)物料一侧界面处的氧交换动态速率，也就是在膜物料一侧的表面上，物料中的氧分子转变成可移动的氧离子的速率；(b)膜中氧离子和电子的扩散速率；(c)渗透侧界面处的氧交换动态速率，即在膜的渗透侧膜中的氧离子转变回氧分子并释放的速率。
Thorogood等人的美国专利US5,240,480(在此引入作为参考)建议通过控制支撑无孔致密层的多孔结构的孔尺寸来控制物料侧界面处氧交换的动态速率。很多文献都描述了具有较高离子和电子导电性能的材料，如Yoshisato等人的美国专利US4,330,633，Yamaji等人的日本公开专利J56[1981]-92103，以及Teraoka和Coworkers的文章，Chem.Letters，The Chem，Soc.of Japan，P503-506(1988)。
金属氧化物膜的典型文献是上述日本专利申请61-21717。当将氧分压较高的含氧气态混合物施加到具有由列举的氧化物形成的致密层的膜的一侧时，在膜表面上将吸附和解离氧，氧变得离子化并通过固体扩散和去离子化，作为氧分压较低的氧气流而在膜的另外一侧结合并解析。
通过氧化物的电子电导性在氧化物内部维持提供该电离/去电离过程电子所必需的电路。这种分离方法被描绘成特别适合于从含有较高分压即高于或等于0.2atm的氧的气流中分离氧。经证实具有氧离子导电性和电子导电性的多成分金属氧化物，其典型的氧离子电导率是0.01ohm-1 cm-1-100ohm-1cm-1，电子电导率约是1ohm-1cm-1-100ohm-1cm-1。
一些多成分金属氧化物在高温主要是或仅仅是氧离子导体。例如(Y2O3)0.1(Zr2O3)0.9，其氧离子电导率在1000℃时是10ohm-1cm-1，而氧迁移数(离子电导率与总电导率的比值)接近1。欧洲专利申请EP0399833A1描述了一种由该氧化物与独立的电子传导相，如铂或另一种贵金属的复合物形成的膜。在分压梯度推动力下，该电子传导相反向提供电子经过该结构，使得氧离子传导经过该复合膜。
另一类多成分金属氧化物表现出：在高温时主要是或仅仅是电子传导，并且它们的氧迁移数接近0。例如在欧洲专利申请EP0,339,833A1中所描述的PrxInyOz。这种材料可以用在具有独立的氧离子传导相，如稳定的ZrO2的复合物膜中。通过把氧分压梯度作为推动力，由这种复合物形成的膜也能用于从含氧流，如空气中分离氧。典型的是，该多成分氧化物电子导体被放置成与氧离子导体紧密接触。
有机聚合物膜也能用于氧分离。然而，由混合导电氧化物形成的膜比聚合物膜提供了显著优越的氧选择性。该改进的选择性的实用价值必须足以抵消与使用由混合导电氧化物形成的膜的建筑及操作工厂有关的较高费用，这类工厂要求有热交换器，高温密封和其它昂贵设备。典型现有的由混合导电氧化物形成的膜并不能表现出足够的透氧性(定义为渗透率与厚度之比)，以证明它们可用于工业氧分离应用中。
众所周知，通过固态膜的透氧性随着膜厚的减少成比例地增加，并且人们已广泛地研究了在力学上稳定的，较薄的膜结构。
例如，Teraoka等人的第二篇文章，Jour.Ceram.Soc.Japan.internationol Ed.Vol 97，pp 458-462，(1989)和J Ceram.Soc.Japan，International Ed，Vol 97，pp 523-529，(1989)，描述了由在多孔混合导电支撑体上沉积-致密无孔混合导电氧化物层(称做致密层)来形成固态分离气体膜。较厚的多孔混合导电支撑体向薄的、较易碎的致密无孔混合导电层提供了力学稳定性。由于各层膜的化学相容性，由在制造和使用中膜所经历的热力学应力所引起的结构损坏被基本上减至最小。基于要限制致密层厚度的考虑，有标准的单层致密的、经过烧结的混合导电片相比，Teraoka和Coworkers认为具有混合导电多孔层和薄混合导电致密层的膜的氧流量可以增加10倍。然而，他们所获得的增加小于2倍。
研究者们仍在对在不损失复合膜的力学和物理相容性下而表现出优异氧流量的固态导电膜进行研究。
本发明涉及在高温下能从含氧物料中分离氧的新型混合导电膜。该膜具有形成在空气中和25-950℃下基本上稳定的基本上是立方钙钛矿结构的结构和组合物，从而与现有的固态膜相比，它显示出较高的氧流量。
尽管人们已经知道膜由混合导电氧化物层组成，但本发明的膜具有形成基本上是立方钙钛矿结构的组合物。该结构表现出较高的氧流量。以较低的浓度向能形成六方相材料的混合金属氧化物中加入特殊的过渡金属稳定了最终的混合导电膜中的立方钙钛矿结构。由此材料形成的膜的氧流量得到增加。
本发明的膜由至少二种不同金属氧化物的混合物形成，其中多成分金属氧化物形成经证实在约高于500℃的温度下具有电子传导性和氧离子传导性的基本上是钙钛矿的结构。这些材料一般称为混合导电氧化物。
合适的混合导电氧化物用下列结构表示：
[A1-xA′x][Co1-y-zByB′z]O3-δ，
式中，A选自Ca，Sr，Ba，和它们的混合物；
A′选自La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；
B选自Fe，Mn，Cr，V，Ti，和它们的混合物；
B′选自于Cu，Ni和它们的混合物；
x不小于约0.0001，不大于约0.1；
y不小于约0.002，小于0.05；
z不小于约0.0005，不大于约0.3；
δ由金属价态决定。
该立方钙钛矿结构在空气中和25-950℃下基本上是稳定的。典型的是，该混合导电氧化物含有不小于约90％的立方钙钛矿结构材料，优选地是不小于约95％立方钙钛矿结构材料，最优选地是不小于约98％立方钙钛矿结构材料。
本发明还涉及由所述混合导体形成的一种或多种膜的应用。该膜合适的应用包括从含氧流体中，特别是空气，或用其它流体稀释了的空气中分离氧气的方法。
本发明涉及由混合导电氧化物形成的新型混合导电膜和使用该膜的方法。该方法中的一种是在高温下从含氧物料中分离氧。该膜是氧离子和电子导体，并且它们具有形成基本上是立方钙钛矿结构的组合物。以较低的浓度向能形成六方相材料的混合金属氧化物中加入特殊的过渡金属稳定了最终的混合导电膜中的立方钙钛矿结构。由该材料形成的膜的氧流量有所增加。更具体地说，一种混合导电膜，已经显示出具有极其高的氧迁移量，其中的膜具有下列组成：
[A1-xA′x][Co1-y-zByB′z]O3-δ，       (式1)
式中，A选自Ca，Sr，Ba，和它们的混合物；A′选自La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；B选自Fe，Mn，Cr，V，Ti，和它们的混合物；B′选自于Cu，Ni和它们的混合物；x不小于约0.0001，不大于约0.1；y不小于约0.002，小于0.05；z不小于约0.0005，不大于约0.3；δ由金属价态决定。其中立方钙钛矿结构在空气中和25-950℃的温度下基本是稳定的。
为了叙述方便，Ca，Sr，Ba和它们的混合物以后称为“A阳离子”，La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；称为“A′阳离子”A阳离子和A′阳离子统统称为“A位阳离子”。类似地，Fe，Mn，Cr，V，Ti和它们的混合物称为“B阳离子”；Cu，Ni，和它们的混合物称为“B′阳离子”； B阳离子和B′阳离子统统称为“B位阳离子”。
通过进一步对氧离子化地迁移经过混合导电氧化物膜的机理的了解，可以更充分地明白申请人的发现。所观察到的传统混合导电膜的氧流量由表面动力学限制和松散扩散限制所控制。表面动力学限制是对由涉及在混合导电膜物料一侧将氧分子转变成可移动的氧离子，而在混合导电膜渗透一侧将氧离子转变回氧分子的。许多步骤中的一步或多步所导致的氧流量的限制。松散扩散限制是对与氧离子扩散通过膜材料相关的氧流量的限定。
基本上由立方钙钛矿相材料组成的膜表现出较高的总氧流量。然而，立方钙钛矿相并不在所有的混合导电氧化物材料中形成，或者如果形成的话，在所要求的形成和操作条件下它们是不稳定的。由六方相材料形成的膜表现出极小的氧流量。因此，为了制造高效膜，膜组合物在操作条件下必须在该膜中保持相当高比例的稳定立方钙钛矿相。
申请人已经发现了可以稳定膜中立方钙钛矿相的组合物，这些膜所具有的组合物以前并不能在空气中和常温及大气压力至分离氧所用条件的范围内保持稳定的立方钙钛矿相。特别是，微量A位阳离子和微量B位阳离子稳定了ABCoO材料中的基本上是立方钙钛矿的结构。另外，加入微量A位阳离子和微量B位阳离子在ABCoO材料中产生了立方钙钛矿结构，否则这种ABCoO材料会产生形成低氧流量膜的六方相材料。
本发明提供了克服这些缺陷的膜，并且可以制造出基本上是立方钙钛矿相的混合导电氧化物结构。由该材料制造的膜表现出较高的总松散扩散率。
所要求的膜包括式1中所描述的组合物，它没有相连的贯穿孔，在空气中和25-950℃下它基本上是稳定的钙钛矿相，并且在操作温度下具有传导电子和氧离子的能力。
本发明的膜由至少两种不同的金属氧化物的混合物形成，其中该多成分金属氧化物经证实在高温下具有电子传导性和氧离子传导性。由于该多成分金属氧化物能在高温下传导电子和氧离子，故适合于本发明的多成分金属氧化物被称为“混合”传导氧化物。式1的组合物代表合适的混合传导氧化物，该组合物在空气中和25-950℃下产生基本是稳定的立方钙钛矿结构。现有技术中所描述的材料，以及与式1组合物极相似，但不同的材料产生主要是六方相或其它相的材料，其中只有很少的立方相存在。这类材料表现出相当低的氧流量。
通式1代表申请人发明的混合导电氧化物；优选的通式为[Sr1-x-x′LaxCax′][Co1-y-zByB′z]O3-δ，式中x′小于约0.01，x大于约0.02，小于约0.1，并且B，B′，y，z和δ如式1中所述；更优选的通式为[Sr1-x-x′LaxCax′][Co1-y-zFeyB′z]O3-δ，式中B′，x，y，z，和δ如式1中所述，并且x′小于约0.01；最优选通式为
[Sr0.95-x′La0.05Cax′][Co1-y-zFeyNiz]O3-δ
[Sr0.95-x′La0.05Cax′][Co1-y-zMnyNiz]O3-δ
[Sr0.95-x′La0.05Cax′][Co1-y-zFeyCuz]O3-δ
[Sr0.95-x′La0.05Cax′][Co1-y-zMnyCuz]O3-δ和它们的混合物，式中0.001＜x′＜0.01，0.0025≤y≤0.01，0.001≤z≤0.05，δ由金属价态决定。
为了确保膜具有足够的机械强度，可以改变材料的厚度。如前面所讨论的，对于一定的膜材料来说，较薄的膜增加了总的松散扩散率，为了利用这一现象，可用一个或多个多孔支撑体支撑薄膜。申请人发明的未支撑的混合导电膜的最小厚度约是0.01mm，优选地为约0.05mm，最优选地为约0.1mm。申请人发明的未支撑的混合导电膜的最大厚度是约10mm，优选地是约2mm，最优选的是约1mm。
申请人发明的带支撑的混合导电膜的最小厚度是约0.0005mm，优选地是约0.001mm，最优选地是约0.01mm。申请人发明的带支撑的混合导电膜的最大厚度是约2mm，优选地是约1mm，最优选的是约0.1mm。
除了氧流量增加外，本发明的膜在温度为25℃-950℃和氧分压为1-约1×10-6大气压(绝对)的条件下是稳定的，它不会发生相变。基本稳定的立方钙钛矿结构包括所有具有不少于90％的立方钙钛矿相材料，优选地是不少于95％的立方钙钛矿相材料，最优选是不少于98％的立方钙钛矿相材料的结构，这些结构在25℃-950℃的温度和氧分压为1-约1×10-6大气压下没有表现出恒定的相变。
立方钙钛矿相的稳定可以认为是由于申请人发现的独特的组合物所引起。相反，以前报道的材料的相变使它们不适合用于经历温度和压力周期变化，或承受在制备和使用它们过程中的条件的设备。例如，具有极相似的组合物的膜，在25-950℃的温度下主要形成六方相结构，并且该材料的氧流量明显比本发明材料低。
通过把含氧物料送入用本膜与第二腔室隔离的第一腔室内；通过在第一腔室内产生过量的氧分压和/或在第二腔室内产生降低的氧分压在第一和第二腔室之间建立正氧分压差；在高于约500℃的温度下使含氧物料与该膜接触以便把含氧物料分离成富氧渗透流和缺氧废流并回收富氧渗透流，本发明膜可用于从含氧物料中回收氧。
当把工艺温度提高到足够高的温度时，第一腔室和第二腔室之间的氧分压差提供了进行分离的推动力，从而使存在于第一腔室内的含氧物料中的氧吸附在膜的第一个表面上，经膜变成离子化并以离子形式迁移经过该膜。把富氧渗透物收集在第二腔室内，在此处通过在第二腔室内的膜第二表面上释放电子将离子氧转变成中性。
通过压缩空气或其它含氧流体可以在第一和第二腔室间产生正氧分压差，使第一腔内达到足够的压力以便在高于或等于约1个大气压的压力下回收富氧渗透流。典型的压力范围为约15psia-250psia，最佳的压力将随含氧物料中的氧含量而变化。为了达到必需的氧分压可以使用传统的压缩机。另外，通过把第二腔室抽真空也能在第一和第二腔室之间产生正氧分压差，从而达到足够的压力以便回收富氧渗透物。第二腔室的抽真空可以用机械方法，用压缩机，泵，等等；化学方法，通过使富氧渗透物反应；热学方法，通过冷却富氧渗透物；或现有技术的其它方法来实现。另外，本发明也可以通过上述手段，采用在减少第二腔室中的氧分压的同时增加第一腔室中的氧分压。在操作过程中，如有必要，或采用向二个腔室供应物料或从二个腔室中抽出产物流的方法。也可以改变相对压力达到最佳地分离氧。
通过将基本上是富氧的渗透物储存在一合适容器中或将其移送至另一工艺可以实现富氧渗透物的回收。富氧渗透物典型地包括纯氧或一般定义为含有至少约90vol％O2，优选地是多于95vol％O2，特别是多于99vol％O2的高纯氧。
提供以下实施例以进一步说明本发明。这些实施例仅用于说明而不是对所附权利要求的限制。
                      实施例
例1
由4.28g La(C2H3O2)3·1.5H2O(来自Alfa，ward Hill，MA)，48.85gSr(C2H3O2)2(来自Aesar，Seabrook NH)和20.07g Co3O4(Aesar)的混合物制备材料组成为[La0.05Sr0.95]CoO3-δ的一混合导电膜。向有800g ZrO2介质，200ml丙酮的500ml聚乙烯振动磨中装入该混合物，并转动70小时。慢慢倒出所得的料浆并在室温下对之真空蒸馏到干燥。在空气中和900℃下于蒸发皿上煅烧该固体达12小时，并在1100℃下再煅烧6小时。向振动磨中加入一份46.47g所得粉末，0.949g聚乙烯醇缩丁醛树脂(Monsanto，st.Louis Mo)，75ml n-己烷和35ml乙醇，以及400g ZrO2介质，并粉磨大约70小时。干燥产物粉末并使之通过325目泰勒筛。对粉末的X射线衍射(XRD)表明该材料是100％的立方钙钛矿相。组成分析表明该材料的组成为[A0.946A′0.054][Co0.99B0.002B′0.003]O3-δ。
用32,000PSi的压力将一份4.06g过筛了的粉末压成一1-3/8″直径的园片。在空气中和405℃下煅烧该园片15分钟，用13个小时将温度提高到1200℃并保持1小时，之后将之冷却到常温。
用500Sic研磨砂将园片的两面抛光至最终厚度为0.97mm。所测得的园片的电阻大约是40ohms。用一1/8″厚的pyrex环把该园片连接在外直径为1英寸的莫来石管上，该园片裸露的表面积为大约2cm2。
将莫来石管，园片，气体处理设备安置在热稳定控制的电加热器上。通过用距管/片结合处大约1cm的连接在莫来石管上的热电偶指示，将该园片在静止空气中加温到960℃，并保持20分钟，然后以1℃/分的速率冷却到850℃。在园片的一侧启动速率为1.0L/min的空气流，并在园片的另一侧启动205cm3/min的氦渗透物料流。用联机的气相色谱仪分析氦渗透物废料，并且调整氦渗透物料流的流量以便使渗透物中的氧含量保持在大约1％。对渗透物进行氮分析以便可能校准漏入渗透流中的任何空气。
用此公式计算膜的氧流量：
qO2＝[qP*(XO2P-0.256*XN2P)*Po/760*273/To]/100
式中qO2＝氧流量(cm3/min)；
    qP＝渗透物抽出流流量(cm3/min)；
    XO2P＝渗透物抽出物中的氧浓度(％)；
    XN2P＝渗透物抽出物中的氮浓度；
    Po＝大气压(mmHg，bs.)；
    To＝常温(度K)。
用此公式将氧流量材料化以便校准膜片厚度的变化
q′O2＝qO2*L
式中，q′O2＝用厚度标准化了的氧流量
             cm3/min-mm
      qO2＝氧流量(cm3/min)
      L＝膜片厚度(mm)
通过用测量的园片面积(cm2)除以用厚度标准化了的氧流量(q′O2)来计算单元面积的氧流量。
在不同的温度和气体流量下对该片的操作性能检测500小时以上。检测数据提供在下面的表1中。对所有的数据点，室温(To)都保持在293°K。空气物料流量保持在1000sccm，530和534小时的检测除外，它们的空气物料流量分别为0和2000sccm。
表1中的数据表明在高温和空气中该材料具有优异的长期稳定性和较高的氧流量。在宽广的空气流范围内(0-2000sccm)保持较高的氧流量。530小时的检测结果特别明显，它表现出从静止空气极快的氧扩散。1和512小时的实验还表明甚至当渗透氧含量较高，而且因此材料上的氧分压差较低时，该材料也具有较高的氧流量。
比较例1(a)
用不同的A位阳离子和B位阳离子量制备标准组成为[La0.05Sr0.95]CoO3-δ的不同，但相似的混合导电膜，该膜不可能形成基本上是立方钙钛矿相材料。
用与在US5,061,682(在此引入做为参考)中所描述的实施例相类似的方法制备该材料。向1.7升去离子水中加入1206.21gSr(NO3)2(Mallinckrodt)，24.44g La2O3(Alfa)和353.76g金属钴粉(Aldrich)。
                            表1时间       膜温         Po    渗透物    渗透物分析            qO2         q′O2hours       Deg.c      mm Hg    sccm       XO2P    XN2P     cc/min     cc/cm2/min1          850      740.2     212        3.354    0.024      6.247       3.1242.5        850      740.2     758        1.259    0.000      8.400       4.2006.5        850      740.2     1010       1.001    0.000      8.899       4.45024         850      744.4     1030       0.970    0.000      8.844       4.42232         850      744.4     1050       0.941    0.000      8.747       4.37347         850      743.7     1050       0.922    0.000      8.562       4.28151         800      743.7     675        0.954    0.000      5.695       2.84853         800      743.7     680        0.937    0.000      5.635       2.81855         750      743.7     473        0.821    0.008      3.426       1.71356         750      743.7     389        0.966    0.009      3.315       1.65872         700      743.4     228        0.885    0.017      1.775       0.88874         800      743.4     663        0.893    0.000      5.234       2.61775         800      743.4     671        0.897    0.000      5.321       2.66076         900      743.4     1070       0.993    0.000      9.393       4.69779         900      742.0     1120       0.976    0.000      9.646       4.82396         900      738.9     1100       1.090    0.009      10.513      5.25798         900      738.9     1130       1.068    0.009      10.582      5.291100        850      738.9     1140       0.850    0.008      8.494       4.247144        850      739.0     990        0.971    0.013      8.419       4.210168        850      743.6     976        0.957    0.013      8.231       4.115192        850      745.0     972        0.959    0.013      8.230       4.115216        850      743.7     988        0.965    0.016      8.396       4.198240        850      740.6     981        0.945    0.016      8.129       4.065264        850      734.4     990        0.948    0.015      8.163       4.082336        850      734.0     996        0.944    0.015      8.174       4.087360        850      734.8     986        0.963    0.012      8.271       4.135384        850      735.6     992        0.978    0.016      8.451       4.226408        850      737.4     992        0.978    0.016      8.472       4.236432        850      732.4     996        0.978    0.009      8.464       4.232504        850      742.0     972        1.008    0.016      8.610       4.305507        850      742.0     1130       0.881    0.015      8.746       4.373509        850      742.0     761        1.248    0.025      8.337       4.169510        850      742.0     447        1.923    0.034      7.550       3.775512        850      742.0     147        4.338    0.133      5.583       2.791528        850      743.6     968        1.008    0.019      8.587       4.293530        850      743.6     973        0.982    0.015      8.416       4.208532        850      743.6     977        1.004    0.015      8.641       4.320534        850      743.6     974        0.978    0.019      8.382       4.191535        850      743.6     972        0.955    0.021      8.162       4.081552        850      740.9     977        0.985    0.020      8.435       4.217557        850      745.3     2040       0.483    0.010      8.687       4.343558        850      745.3     1520       0.637    0.014      8.533       4.267560        850      745.3     504        1.696    0.033      7.538       3.769577        900      750.3     505        1.810    0.024      8.128       4.064579        900      750.3     999        1.070    0.012      9.510       4.755581        900      750.3     1510       0.754    0.009      10.128      5.064583        900      750.3     2040       0.590    0.000      10.739      5.370
用一轻便的喷雾干燥器对上述陶瓷前体溶液喷雾干燥。合适的轻便喷雾干燥器是Columbia，Md的Niro雾化器。该喷雾干燥器包括一个转速能达到40,000rpm的离心雾化器。该雾化器位于干燥室的顶部，该干燥室内径为2英尺7英寸，柱体高度为2英尺，锥底为60°。离心雾化器和干燥室用不锈钢制做。干燥室与空气电加热器相连以便向干燥室内提供干燥空气。干燥空气由位于干燥室下游的鼓风机抽过干燥室。喷雾干燥器包括容纳来自于干燥室底部的干燥空气和干燥产物的旋风分离器。该旋风分离器从排出的干燥空气中分离出干燥产物。该旋风分离器的底部包括能使干燥粒子重力沉降到垂直取向的使空气温度保持在大约300°-450℃的管式炉中的一个出口。干燥粒子在该管式炉中热分解。管式炉具有足够的高度以便向自由降落的粒子提供大约为0.5-2.0秒的停留时间。管式炉的底部与收集陶瓷粒子的收集室相连。
将上述的陶瓷前体溶液以大约1.8升/小时的流量引入喷雾干燥室中。以大约30,000RPM旋转的离心雾化器将该前体溶液分散成直径大约为20-50微米的液滴。通过干燥室和旋风器的空气流大约是35-40标准立方英尺/分钟。进入干燥室的空气被预热到约375℃。当小液滴被迫对着干燥室的底部对流时，它们完全脱水达到脱水的临界状态，结果它们的直径减少到大约10.0微米或更小。在干燥室底部的干燥气体的温度大约是125℃，它确保基本上所有的水从喷雾干燥器中的粒子中除去。然后在旋风分离器中干燥粉末与干燥空气相互分离。分离后的粉末由于重力降落到被预热到约490℃的管式炉中。在炉中的粒子停留时间大约是0.5-2秒。管式炉中的温度促使硝酸根离子和各个粒子中的氧化物间发生阴离子氧化还原放热反应。燃烧的副产品(CO2和水蒸汽)通过系统并排放，同时反应后的粒子落入收集罐中，收集到大约60.0g的粒子，其平均粒子尺寸大约是5.0微米。
分析最终的产物，XRD结果表明该材料在结构上是六方的，所具有的组成是[A0.976A′0.024][Co0.999B0.0002B′0.001]O3-δ。用该粉末压制成二块园片，并用前述的方法制备和测试。测试结果包括在下面的表2中。如实例1那样，室温保持在293°K，对于实施例1(a)(i)，空气物料流量是500sccm，对于实施例1(a)(ii)，它是510sccm。
                      表2实施例1(a)(i)  膜厚＝1.020mm时间  温度  大气压P  渗透物    渗透物分析        qO2        q′O2小时   ℃     mmHg    sccm    ％O2   ％N2    cc/分钟    cc/cm2/分钟1    800    740.0    492    0.234    0.817     0.113      0.0574    800    740.0    314    0.354    1.238     0.108      0.054实施例1(a)(ii)  膜厚＝1.000mm时间  温度  大气压P  渗透物     渗透物分析       qO2     q′O2小时  ℃     mmHg     sccm     ％O2    ％N2  cc/分钟   cc/cm2/分钟1    800    740.0     310     0.536    1.847    0.178      0.0894    800    740.0     310     0.840    2.826    0.328      0.164
实施例2和2(a)
利用不同数量的A位阳离子和B位阳离子制备标准组成为[La0.05Sr0.95]CoO3-δ的二种混合导电粉末以证实组成对立方钙钛矿结构形成的影响。除了将起始材料的比例稍微调整外，用与实例1和1(a)相类似的方法制备该材料。用XRO分析该最终过筛后的粉末。
用实例1中所述的方法制备实施例2的产品，它的组成为[A0.945A′0.055][Co0.97B0.021B′0.003]O3-δ，并是立方钙钛矿结构。
用实例1(a)中所述的方法制备对比实施例2(a)的产品，它的组成为[A0.944A′0.056][Co0.999B0.0002B′0.001]O3-δ，并且是六方结构。

Claims (10)

1.一种包括在空气和25-950℃的温度下基本稳定的，基本上是立方钙钛矿结构的组合物的膜，该组合物用下列经验通式表示：
[A1-xA′x][Co1-y-zByB′z]O3-δ，
式中，
A选自Ca，Sr，Ba，和它们的混合物；
A′选自La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；
B选自Fe，Mn，Cr，V，Ti，和它们的混合物；
B′选自于Cu，Ni和它们的混合物；
x不小于约0.0001，不大于约0.1；
y不小于约0.002，小于0.05；
z不小于约0.0005，不大于约0.3；
δ由金属价态决定。
2.根据权利要求1的膜，其中所说的组合物含有不少于90％(的立方钙钛矿相材料。
3.根据权利要求1的膜，其中A位阳离子用下列经验通式表示：
[Sr1-x-x′LaxCax′]，式中，x大于约0.02，小于约0.1；x′小于约0.01。
4.根据权利要求3的膜，其中，B包括Fe。
5.根据权利要求1的膜，其中所说的组合物选自
[Sr0.95-x′La0.05Cax′][Co1-y-zFeyNiz]O3-δ，
[Sr0.95-x′La0.05Cax′][Co1-y-zMnyNiz]O3-δ，
[Sr0.95-x′La0.05Cax′][Co1-y-zFeyCuz]O3-δ，
[Sr0.95-x′La0.05Cax′][Co1-y-zMnyCuz]O3-δ，以及它们的混合物，式中
x′大于约0.001，小于约0.01；
y不小于0.0025，不大于0.01；
z不小于0.001，不大于约0.05；
δ由金属价态决定。
6.一种膜的应用，所说的膜包括基本是立方钙钛矿结构的用下例经验通式表示的组合物
[A1-xA′x][Co1-y-zByB′z]O3-δ，
式中
A选自Ca，Sr，Ba，和它们的混合物；
A′选自La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；
B选自Fe，Mn，Cr，V，Ti，和它们的混合物；
B′选自于Cu，Ni和它们的混合物；
x不小于约0.0001，不大于约0.1；
y不小于约0.002，小于0.05；
z不小于约0.0005，不大于约0.3；
δ由金属价态决定。
7.一种分离氧的方法，该方法包括在25-950℃之间的温度下让包括基本是立方钙钛矿结构的用下列经验通式表示的组合物的膜与合适的含氧流体接触，
[A1-xA′x][Co1-y-zByB′z]O3-δ，
式中
A选自Ca，Sr，Ba，和它们的混合物；
A′选自La，Y，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Th，U，和它们的混合物；
B选自Fe，Mn，Cr，V，Ti，和它们的混合物；
B′选自Cu，Ni和它们的混合物；
x不小于约0.0001，不大于约0.1；
y不小于约0.002，小于0.05；
z不小于约0.0005，不大于约0.3；
δ由金属价态决定。
8.根据权利要求7的方法，其中所说的流体包括空气。
9.一种流体分离设备采用至少一种权利要求1的膜。
10.权利要求9的流体分离设备用于从含氧流体中分离氧。
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EP0705790B1 (en) 2000-03-15
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US5702999A (en) 1997-12-30
DE69515586D1 (de) 2000-04-20
DE69515586T2 (de) 2001-04-26
JPH08173776A (ja) 1996-07-09
ES2145224T3 (es) 2000-07-01
US5788748A (en) 1998-08-04
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US5648304A (en) 1997-07-15
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