CN101506122B - 复合氧离子传送膜 - Google Patents

复合氧离子传送膜 Download PDF

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CN101506122B
CN101506122B CN200780031388XA CN200780031388A CN101506122B CN 101506122 B CN101506122 B CN 101506122B CN 200780031388X A CN200780031388X A CN 200780031388XA CN 200780031388 A CN200780031388 A CN 200780031388A CN 101506122 B CN101506122 B CN 101506122B
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electronics
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CN101506122A (zh
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N·纳加巴沙纳
J·A·莱恩
G·M·克里斯蒂
B·A·范哈泽尔
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Praxair Technology Inc
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Praxair Technology Inc
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Abstract

一种复合氧离子传送膜(1)，其具有致密层(10)、多孔载体层(12)、位于多孔载体层(12)和致密层(10)之间的任选的中间多孔层(14)以及覆盖在致密层(10)上的任选的表面交换层(16)。致密层(10)具有电子相和离子相。该离子相包括氧化钪掺杂的、钇或者铈稳定的氧化锆。该电子相包括含有镧、锶、铬、锰和钒以及任选的铈的金属氧化物。多孔载体层(12)包括用钇、钪、铝或者铈或者其混合物部分稳定的氧化锆。如果使用，中间多孔层(14)包含与致密层相同的离子相和电子相。表面交换层(16)由电子相和离子相形成，该电子相是镧和锶以及还包含锰或者铁的金属氧化物，该离子相是氧化钪掺杂的、钇或者铈稳定的氧化锆。

Description

复合氧离子传送膜
发明领域
本发明涉及一种复合氧离子传送膜，其中具有电子和离子传导相的致密层被承载在多孔载体层上。更具体的，本发明涉及这样一种复合氧离子传送膜，其中电子相是含钒的钙钛矿类金属氧化物，离子相是稳定的氧化锆，多孔载体层由部分稳定的氧化锆形成。
发明背景
已经提出了复合氧离子传送膜的多种用途，包括使氧离子传送通过这样的膜，从含氧的供料中分离氧来生产基本纯净的氧气。例如，每种膜可以用于燃烧装置中来负载氧-燃料燃烧或者用于涉及合成气体生产的部分氧化反应。
在这样的膜中，氧离子的传送主要发生在致密层中，该致密层允许氧离子和电子二者在高温传送。来自含氧的供料中的氧在膜的一个表面上电离，所形成的氧离子被驱动通过致密层并出现在其的对侧，重新结合成元素氧。在该重新结合中，电子被放出并通过膜送回来电离氧。
这样的膜可以使用两个相，传导氧离子的离子相和传导电子的电子相。为了使得膜对于离子传送的阻抗最小，这样的膜被制造得尽可能薄，并且承载在多孔载体层上。所形成的复合氧传送膜可以被制作成平面元件或者管状，在其中致密层位于管子的内部或者外部。
复合氧离子传送膜的一个例子公开在U.S.5240480中，其具有承载在两个多孔层上的致密层。该致密层可以由离子传导相(其包含钇稳定的氧化锆)和电子传导相(其由铂或者另一种贵金属形成)形成。邻近致密层的多孔层是活性的并且能够传导氧离子和电子。其他的多孔层可以是钇稳定的氧化锆或者钙稳定的氧化锆。
U.S.5478444公开了一种能够传送氧离子和电子的两相材料。氧离子传导相可以是混有钇稳定剂和掺杂剂(其可以是铁或者钴)的金属铈氧化物。电子传导相可以是钙钛矿(其包含镧、锶、镁和钴或者镧、锶钴和铁)。
U.S.5306411公开了一种双相膜，其具有由Sc2O3稳定的氧化锆形成的离子传导相。电子传导相可以是含例如镧锶，铁，铬和钒的钙钛矿材料。所形成的致密层可以承载在atria稳定的氧化锆上。
所有复合氧离子传送膜中存在的问题是强度或耐久性。这个问题部分是当这样的膜用于与氧-燃料燃烧和在反应器中时，由于高温而出现的。因为致密层非常薄，因此它必须被承载。从而，在致密层的热膨胀、它的多孔载体和任何的中间活性多孔层之间必须有一个紧密的配合。此外，当这样的膜经历高氧气分压时，存在着进一步的问题。高氧气分压是在燃烧装置中产生的，这是因为氧气一从膜中出现，它就会被与燃料的反应而消耗。这导致了由于高还原性环境引起的化学膨胀。此外，当用作载体时，钙钛矿特别易于出现称为“蠕变(creep)”的现象，在该现象中材料将在延长的热和机械应力下破坏。
如同将要讨论的那样，本发明提供一种复合氧离子传送膜元件，其比上述现有技术的复合膜更结实，并且其特别适于高温和化学膨胀的环境。
发明概述
本发明提供一种复合氧离子传送膜，其包含具有电子相和离子相的致密层。作为此处和权利要求中所用的，术语“致密”层表示一种层，在其中陶瓷层没有连接的直通孔隙。
根据本发明，电子相是(LauSrvCe1-u-v)wCrxMnyVzO3-5，其中u是约0.7-约0.9，v是约0.1-约0.3，(1-u-v)大于或者等于0，w是约0.94-约1，x是约0.67-约0.77，y是约0.2-约0.3，z是约0.015-约0.03，和x+y+z＝1。离子相是Zrx′Scy′Az′O2-δ，其中y′是约0.08-约0.15，z′是约0.01-约0.03，x′+y′+z＝1，A是Y或者Ce或者Y和Ce的混合物；
该致密层承载在多孔载体层上。多孔载体层由Zrx″Ay″O2-δ形成，其中y″是约0.03-约0.05，x″+y″＝1，A是Y或者Sc或者Al或者Ce或者Y、Sc、Al和Ce的混合物。
用于本发明的材料比现有技术具有许多的优点。本发明一个主要的优点是所有的材料具有非常接近的热膨胀匹配性，因为它们全部都具有非常低的线性膨胀。此外，所有的材料具有有限的化学膨胀，这对于选择作为致密层的电子相的钙钛矿来说是特别重要的。就这点而言，与使用金属相反(因为必须使用贵金属来防止氧化)，使用这样的钙钛矿是特别有优势的。使用贵金属明显的问题是费用。同时，含钒的钙钛矿是非常难以烧结的材料。但是，如同下面将要讨论的那样，本发明人在此已经解决了允许其用于氧传送膜中这样的问题。此外，由于使用了部分稳定的氧化锆，因此载体是特别结实的。
一种多孔中间层可以被提供在致密层和多孔载体层之间。这样的多孔中间层可以包括致密层的电子相和离子相。此外，可以提供覆盖致密层的表面交换层来使得该致密层位于该表面交换层和多孔中间层之间。表面交换层可以合并有另外的电子导体和另外的离子导体，该另外的电子导体包括(Lax″′Sr1-x″′)y″′MO3-δ，其中x″′是约0.2-约0.8，y″′是约0.95-1，M＝Mn、Fe，该另外的离子导体包括Zrx ivScy ivAz ivO2-δ，其中yiv是约0.08-约0.15，ziv是约0.01-约0.03，xiv+yiv+ziv＝1和A＝Y、Ce。
优选离子相构成致密层和中间多孔层每一个的约35-65体积％，剩余的为电子相；和该另外的离子导体构成表面交换层的约35体积％-约65体积％，剩余的为另外的电子导体。优选地，该离子相构成致密层和中间多孔层每一个的约50体积％，剩余的为电子相；和该另外的离子导体构成表面交换层的约50体积％，剩余的为电子导体。
优选地，在致密层中电子相是(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ和离子相是Zr0.89Sc0.1Y0.01O2-δ。多孔载体层优选由Zr0.97Y0.03O2-δ形成。如果使用，则在表面交换层中，另外的离子导体是Zr0.89Sc0.1Y0.01O2-δ和另外的电子导体是La0.8Sr0.2FeO3-δ。在本发明一种特别优选的实施方案中，该多孔中间层具有约20微米-约60微米的第一厚度，约0.1微米-约0.5微米的第一平均孔径和约40％-约60％的第一孔隙率。在这样的实施方案中，多孔载体层可以优选具有约1mm-约2.5mm的第二厚度，约2微米-约5微米的第二平均孔径和约40％-约60％的第二孔隙率。覆盖的多孔载体层可具有约10微米-约25微米的第三厚度，约0.1微米-约0.5微米的第三平均孔径和约40％-约60％的第三孔隙率。
要提到的是，作为此处和权利要求中所用的，术语“孔径”表示通过本领域公知的技术-定量立体线交叉分析(quantitativestereological line intersection analysis)所测量的平均孔直径。
附图说明
虽然权利要求的规格结论明确的指出了申请人认为的他们的发明的主旨，但是可以相信当参考附图时，本发明将变得更好理解，在附图中，该单个的图是本发明的复合氧离子传送膜的扫描电镜图。
发明详述
该单个的图表示了本发明的氧离子传送膜1。氧离子传送膜1具有承载在多孔载体12上的致密层10。可以具有任选的中间多孔层14和表面交换层16。
致密层10的作用是从曝露于氧离子传送膜10的一个表面上的含氧的供料中分离氧气，该致密层包含电子和离子传导相。如上所述，电子相是(LauSrvCe1-u-v)wCrxMnyVzO3-5，其中u是约0.7-约0.9，v是约0.1-约0.3，(1-u-v)大于或者等于0，w是约0.94-约1，x是约0.67-约0.77，y是约0.2-约0.3，z是约0.015-约0.03，和x+y+z＝1。离子相是Zrx′Scy′Az′O2- δ，其中y′是约0.08-约0.15，z′是约0.01-约0.03，x′+y′+z′＝1，A是Y或者Ce或者Y和Ce的混合物。要提到的是，由于数量(1-u-v)可以等于0，铈在本发明的电子相中可以不存在。
多孔载体层12由Zrx″Ay″O2-δ形成，其中y″是约0.03-约0.05，x″+y″＝1，A是Y或者Sc或者Al或者Ce或者Y、Sc、Al和Ce的混合物。
氧离子传送膜1被明确设计来用于与氧-燃料燃烧相关的应用以及涉及化学反应的应用中。但是，本发明的应用不限于这样的用途。但是，当应用涉及燃料燃烧时，中间多孔层14的使用通过提供高表面面积(在这里燃料可以在部分或者完全形成氧化产物的情况下与氧或者氧离子反应)而提高了燃料在界面处氧化的速率。氧离子通过该多孔层的混合的传导基质朝着多孔载体12扩散，并且与燃料(其从多孔载体12向内扩散到该多孔中间层14中)进行反应。优选多孔中间层14是由与致密层10相同的电子相和离子相形成的。
本发明的任何实施方案可以有利的包括覆盖在多孔中间层(如果同样使用)的对面的致密层的表面交换层16。表面交换层16通过提高致密层10的表面面积而提高了表面交换率，同时提供了用于所形成的氧离子通过混合的传导氧化物相扩散到致密层10的路径以及氧分子通过开孔空间扩散到致密层10的路径。表面交换层16因此减少了在表面交换方法中的驱动力的损失，并由此提高了可实现的氧流量。如上所示，其还可以是一种含有电子导体和离子导体的两相混合物，电子导体包括(Lax″′Sr1-x″′)y″′MO3-δ，其中x″′是约0.2-约0.8，y″′是约0.95-1，M＝Mn、Fe，离子导体包括Zrx ivScy ivAz ivO2-δ，其中yiv是约0.08-约0.15，ziv是约0.01-约0.03，xiv+yiv+ziv＝1和A＝Y、Ce。
在本发明一种特别优选的实施方案中，致密层10包括电子相和离子相，该电子相包括(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ，离子相包括Zr0.89Sc0.1Y0.01O2-δ。在这样的实施方案中，多孔载体层12由Zr0.97Y0.03O2-δ形成，表面交换层含有的离子导体包括Zr0.89Sc0.1Y0.01O2-δ，电子导体包括La0.8Sr0.2FeO3-δ。优选多孔中间层14具有约20微米-约60微米的厚度，约0.1微米-约0.5微米的平均孔径和约40％-约60％的第一孔隙率。多孔载体层12具有约1mm-约2.5mm的厚度，约2微米-约5微米的平均孔径和约40％-约60％的孔隙率。表面交换层16具有约10微米-约25微米的厚度，约0.1微米-约0.5微米的平均孔径和约40％-约60％的孔隙率。
作为制作本发明的氧传送膜元件的一个例子，首先用喷雾造粒的钇稳定的氧化锆粉末(具有化学式Zr0.97Y0.03O2-δ，下文中称为“YSZ粉末”)来制作多孔载体层12。这样的粉末的粒度是d50＝0.6μm(约50％的该粒子具有低于0.6μm的粒度)。然后将该粉末与玻璃碳(具有d50为约0.4-约12μm的粒度)和淀粉(具有d50为约34μm的粒度)进行湿混合。该混合物包含约10％的玻璃碳(glassy carbon)、15％淀粉和剩余量的钇稳定的氧化锆粉末。为了密封的目的，理想的是该氧传送膜元件在端部是非多孔性的。同样，将该YSZ粉末与粘合剂例如PVB(聚乙烯缩丁醛，其可以获自Sigma-Aldrich，3050 Spruce Street，St.Louis，MO63103)进行混合，然后倒入等静压模具中。该等静压模具可以是20mm厚的柔性管，具有约24.75mm的内径和内部17.75mm直径的心轴。此后，将YSZ粉末、碳淀粉和粘合剂的混合物倒入该模具中，然后将另外量的YSZ粉末和粘合剂的混合物单独倒入该模具。作为结果，载体层12的端部将是非多孔性的，中心部分将是多孔的。
然后将使该模具经历约20ksi的静水压来形成生坯管。在该生坯管形成之后，然后该管在1000℃烧制4小时来达到对于进一步的处理来说合理的强度。烧制之后，可以检测所形成的管的孔隙率、渗透性/弯曲度并存放在约60℃的干燥炉中。
在形成生坯管之后，然后形成中间多孔层14。制备约34g的粉末混合物，其具有电子相和离子相以及各自具有化学式(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ(“LSCMV”)和Zr0.89Sc0.1Y0.01O2-δ(“YScZ”)，目的是该混合物包含相同体积比例的LSCMV和YScZ。将100g甲苯、20g上述类型的粘合剂、400g的1.5mm直径的YSZ研磨介质加入所述的混合物中。然后将该混合物研磨约6小时来形成浆体(d50为约0.34μm)。然后加入约6g炭黑(具有约d50＝0.8μm的粒度)到该浆体中并研磨另外的2小时。将另外的10g甲苯和约10g另外的粘合剂加入到该浆体中并混合约1.5到约2小时。然后将上面所形成的生坯管的内壁如下来进行涂覆：倒入所述的浆体，保持5s一次，并将残余物倒回瓶子中。然后干燥该涂覆的生坯管，并在850℃空气中烧制1小时来将粘合剂烧掉。
然后施加致密层10。制备约40g重量的混合物，其包含上述的用于形成中间多孔层14相同的粉末，除了LSCMV与YScZ的体积比例约是40/60。然后将2.4g的硝酸钴{Co(NO3)2·6H2O}，95g甲苯，5g乙醇，20g上述的粘合剂，400g的1.5mm直径的YSZ研磨介质加入到该混合物中并研磨约10小时来形成浆体(d50～0.34μm)。再次，将约10g甲苯和约10g粘合剂加入到该浆体中并混合约1.5到约2小时。然后如下来涂覆管的内壁：倒入所述的浆体，保持10s一次，并将残余物倒回瓶子中。然后在受控环境中烧制所述的层之前，将该管干燥保存。
然后将该涂覆的生坯管放在平管炉中的C定位器(setter)上，并将多孔用硝酸铬填充的多孔氧化铝管放在靠近该涂覆管的位置来用铬蒸汽使环境饱和。将该管在静态空气中加热到约800℃来烧掉粘合剂，并将环境切换为饱和的氮气混合物(氮气和水蒸汽)的氛围，其包含约4体积％的氢气来使得含钒的电子传导钙钛矿适当的烧结。将该管在1400℃保持8小时，然后在氮气中冷却来完成材料烧结。检测该烧结管的氦气泄漏率，其应当低于10-7Pa。
然后施加表面交换层16。制备一种粉末混合物，其包含约35的等量的离子相和电子相，并各自具有化学式Zr0.89Sc0.1Y0.01O2-δ和La0.8Sr0.2FeO3-δ。将约100g甲苯、20g上述类型的粘合剂、约400g的1.5mm直径的YSZ研磨介质加入该混合物中，并将所形成的混合物研磨约14小时来形成浆体(d50～0.4μm)。将约6g的炭黑加入到该浆体中并研磨另外2小时。然后将约10g甲苯和约10g粘合剂的混合物加入到该浆体中并混合约1.5到约2小时。然后如下来涂覆管的内壁：倒入所述的浆体，保持约10s两次，并将残余物倒回瓶子中。然后将该涂覆管干燥，并在1100℃空气中烧制2小时。
所形成的管具有在上述范围内的优选的厚度、孔径和孔隙率，即，多孔中间层14具有约25微米的厚度，约0.1-约0.5微米的平均孔径和约40％-约60％的孔隙率。多孔载体层12具有约2.1mm的厚度，约2-约5微米的平均孔径和约45％的孔隙率。表面交换层16具有约14微米的厚度，约0.1-约0.5微米的平均孔径和约40％-约60％的孔隙率。已经发现这样的管子能够经受住这样的操作循环：在1512小时的操作过程中循环20-40个周期，每个循环包括冷却到约25℃的温度并加热到约1000℃的温度。
应当提到的是在本发明的任何实施方案中，用于沉积中间和致密分离层14和10的铬铁矿/氧化锆浆体的粒度应当在约0.3和约0.35μm的范围内。由这样的浆体制作的膜表现出在两相之间最小的反应性以及匹配多孔氧化锆载体的收缩性。
优选硝酸钴被用作烧结助剂来增密致密层10。优选多孔氧化铝管具有约0.5mm的孔径和约60％的孔隙率，约12.75mm的直径和约2mm的厚度。每个氧化铝管包含约10重量％的硝酸铬。
虽然已经参考优选的实施方案对本发明进行了描述，但是，如本领域技术人员将想到的那样，可以进行诸多的改变、添加和删减而不脱离在附加的权利要求中所提供的本发明的主旨和范围。

Claims (10)

1.一种复合氧离子传送膜，其包含：
具有电子相和离子相的致密层；
所述的电子相是(LauSrvCe1-u-v)wCrxMnyVzO3-5，其中u是0.7-0.9，v是0.1-0.3，(1-u-v)大于或者等于0，w是0.94-1，x是0.67-0.77，y是0.2-0.3，z是0.015-0.03，和x+y+z＝1；
所述的离子相是Zrx′Scy′Az′O2-δ，其中y′是0.08-0.15，z′是0.01-0.03，x′+y′+z′＝1，A是Y或者Ce或者Y和Ce的混合物；
多孔载体层，所述的多孔载体层由Zrx″Ay″O2-δ形成，其中y″是0.03-0.05，x″+y″＝1，A是Y或者Sc或者Al或者Ce或者Y、Sc、Al和Ce的混合物。
2.权利要求1的复合离子传送膜，其进一步包含：
位于致密层和多孔载体层之间的多孔中间层；并且
该多孔中间层包括电子相和离子相。
3.权利要求1的复合离子传送膜，其进一步包含：
表面交换层，其覆盖致密层来使得该致密层位于该表面交换层和多孔中间层之间；
所述的表面交换层包括另外的电子导体和另外的离子导体，该另外的电子导体包括(Lax″′Sr1-x″′)y″′MO3-δ，其中x″′是0.2-0.8，y″′是0.95-1，M＝Mn、Fe，该另外的离子导体包括Zrx ivScy ivAz ivO2-δ，其中yiv是0.08-0.15，ziv是0.01-0.03，xiv+yiv+ziv＝1和A＝Y、Ce。
4.权利要求3的复合离子传送膜，其中：
该离子相构成致密层和中间多孔层每一个的35-65体积％，剩余的为电子相；和
该另外的离子导体构成表面交换层的35体积％-65体积％，剩余的为另外的电子导体。
5.权利要求4的复合离子传送膜，其中：
该离子相构成致密层和中间多孔层每一个的50体积％，剩余的为电子相；和
该另外的离子导体构成表面交换层的50体积％、剩余的为电子导体。
6.权利要求1的复合离子传送膜，其中：
电子相是(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ；和
离子相是Zr0.89Sc0.1Y0.01O2-δ。
7.权利要求2的复合离子传送膜，其中：
电子相是(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ；和
离子相是Zr0.89Sc0.1Y0.01O2-δ。
8.权利要求6或者7的复合离子传送膜，其中所述的多孔载体层由Zr0.97Y0.03O2-δ形成。
9.权利要求5的复合离子传送膜，其中：
电子相是(La0.825Sr0.175)0.97Cr0.76Mn0.225V0.015O3-δ；离子相是Zr0.89Sc0.1Y0.01O2-δ；
所述的多孔载体层由Zr0.97Y0.03O2-δ形成；另外的离子导体是Zr0.89Sc0.1Y0.01O2-δ；和另外的电子导体是La0.8Sr0.2FeO3-δ。
10.权利要求9的复合离子传送膜，其中：
多孔中间层具有20微米-60微米的第一厚度，0.1微米-0.5微米的第一平均孔径和40％-60％的第一孔隙率；
多孔载体层具有1mm-2.5mm的第二厚度，2微米-5微米的第二平均孔径和40％-60％的第二孔隙率；和
所述的表面交换层具有10微米-25微米的第三厚度，0.1微米-0.5微米的第三平均孔径和40％-60％的第三孔隙率。
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US20080047431A1 (en) 2008-02-28
US7556676B2 (en) 2009-07-07
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CA2660359C (en) 2011-11-01
WO2008024405A2 (en) 2008-02-28
BRPI0715970A2 (pt) 2013-08-06
CN101506122A (zh) 2009-08-12
CA2660359A1 (en) 2008-02-28
KR101395977B1 (ko) 2014-05-16
WO2008024405A3 (en) 2008-04-10

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