CN114728266A - 用于制备氧化铝负载的钙钛矿型氧化物组合物的方法、氧化铝负载的钙钛矿型氧化物组合物及其用途 - Google Patents
用于制备氧化铝负载的钙钛矿型氧化物组合物的方法、氧化铝负载的钙钛矿型氧化物组合物及其用途 Download PDFInfo
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- CN114728266A CN114728266A CN202080078850.7A CN202080078850A CN114728266A CN 114728266 A CN114728266 A CN 114728266A CN 202080078850 A CN202080078850 A CN 202080078850A CN 114728266 A CN114728266 A CN 114728266A
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- alumina
- water
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- 238000001354 calcination Methods 0.000 claims description 29
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- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明涉及一种用于制备氧化铝负载的钙钛矿型氧化物组合物的方法、氧化铝负载的钙钛矿型氧化物组合物以及这种氧化铝负载的钙钛矿型氧化物组合物在排放控制应用的催化体系中的用途。
Description
技术领域
本发明涉及用于制备氧化铝负载的钙钛矿型氧化物组合物的方法、氧化铝负载的钙钛矿型氧化物组合物及其在排放控制应用的催化体系中的用途。
背景技术
为了减少稀燃发动机的排放气体中的NOx含量,需要指定的NOx后处理系统。这是因为在一般的氧化条件下不可能如在接近化学计量条件下操作的三效催化剂中那样将NOx还原为N2。因此,已开发了一种特殊的排放气体后处理催化剂,其包含能够储存NOx(例如在稀薄条件下为硝酸盐/亚硝酸盐的方式)的材料。通过施用短少化学计量或富集的操作条件,则可以将储存的NOx转化为氮气,并且使储存材料再生。这种催化剂通常被称为(稀薄)NOx捕获催化剂。NOx捕获催化剂可以被安置在基于沸石的选择性催化还原(“SCR”)催化剂的上游,所述选择性催化还原催化剂在较高的温度下非常有效。
NOx捕获催化剂通常含有CeO2作为储存组分,该储存组分尤其用于在低温至中温范围内储存NOx。缺点是在除NOx步骤期间,因此在富集的排放气体组合物进行再生期间,由于二氧化铈的氧化还原活性而消耗了大部分的还原剂。这样因Ce4+还原为Ce3+而导致严重的燃料损失。
因此,需要开发能够在低温至中温范围内储存NOx而且在操作条件下不具有氧化还原活性的材料。
具有分子式ABO3的非氧化还原活性钙钛矿(其中A为包括稀土金属、碱土金属、碱金属、Pb2+和Bi3+的阳离子,而B为包括过渡金属的阳离子)是一种有吸引力的替代品。然而,这些化合物在块体状态下通常不具有与NOx反应所需的表面积。
US2012/0046163A1中公开了钙钛矿及其在排放气体的排放催化剂体系中的用途。在该专利中,公开了镧基钙钛矿在由氧化铝或羟基氧化铝制成的载体上的复合材料。该复合材料是通过沉淀方法制成的。该方法产生了优于现有技术的钙钛矿。在US2012/0046163中,其第3段教导了所需的钙钛矿低结晶度及其重要性,其中指出将钙钛矿尽可能精细地分散在载体上,亦即以细颗粒的形式提供钙钛矿。然而,特定催化应用所需的低结晶度无法通过US2012/0046163中教导的方法获得。
US 4921829公开了一种用于制备负载的钙钛矿混合氧化物的两步法。在实施例5的第一步骤中,由γ-氧化铝和硝酸镧制得LaAlO3粉末。将该LaAlO3与钙钛矿前体化合物的水溶液混合,进行干燥并煅烧。因此,LaAlO3与钙钛矿材料的催化剂成分共存。
US 5882616公开了一种用于制备负载的钙钛矿混合氧化物的两步法。在实施例1的第一步骤中,用硝酸镧浸渍γ-氧化铝。用钙钛矿前体化合物的水溶液浸渍该稳定的氧化铝三次,进行干燥并煅烧。尽管没有报道微晶尺寸,但X射线衍射图中相对尖锐的反射表明钙钛矿微晶大于5nm。
因此,仍然需要开发一种在氧化铝载体上具有钙钛矿结构的均匀钙钛矿型氧化物复合材料,其具有改进的特性。
发明内容
根据本发明的第一方面,提供了一种用于制备氧化铝负载的钙钛矿型氧化物组合物的方法,所述方法包括以下步骤:
i)提供掺杂氧化铝,所述掺杂氧化铝包含:
a.氧化铝和稀土金属氧化物,或
b.氧化铝和碱土金属氧化物,或
c.氧化铝以及稀土金属氧化物和碱土金属氧化物的混合物,
其中通过包括至少以下步骤的方法提供所述掺杂氧化铝:
A)制备勃姆石悬浮液,所述勃姆石悬浮液包含勃姆石;
B)制备盐水溶液,所述盐水溶液包含:
a.稀土金属盐,或
b.碱土金属盐,或
c.稀土金属盐和碱土金属盐的混合物;
C)将所述勃姆石悬浮液与所述盐水溶液相结合以形成勃姆石盐混合物;
D)干燥勃姆石盐混合物以形成干燥的勃姆石盐混合物;以及
E)煅烧干燥的勃姆石盐混合物以形成掺杂氧化铝;
ii)用浸渍水溶液浸渍提供的掺杂氧化铝以形成经浸渍的掺杂氧化铝,所述浸渍水溶液包含以下的一种或混合物:水溶性稀土金属盐、水溶性碱土金属盐、水溶性碱金属盐、水溶性Pb2+盐、水溶性Bi3+盐和水溶性过渡金属盐;以及
iii)煅烧经浸渍的掺杂氧化铝以获得氧化铝负载的钙钛矿型氧化物组合物。
勃姆石定义为具有分子式AlOOH*xH2O(其中x在0至0.5之间)的任何氧化铝,包括勃姆石和拟勃姆石。
勃姆石悬浮液可以进一步包含二氧化硅、二氧化钛、钛或锆的水溶性盐、或者它们的混合物。
勃姆石悬浮液包含勃姆石前体和至少水,勃姆石前体和至少水的比例优选为2:98至20:80。勃姆石悬浮液任选地包含pH调节添加剂,例如羧酸或氨。
更优选地,通过Al-醇盐的水解制备勃姆石悬浮液。
用于制备掺杂氧化铝的盐水溶液优选地至少包含水、以及水溶性稀土金属盐、水溶性碱土金属盐或它们的混合物。稀土金属盐优选为具有原子序数57至60的元素的乙酸盐或硝酸盐,最优选为乙酸镧。碱土金属盐优选为碱土金属乙酸盐或碱土金属硝酸盐。碱土金属盐优选为Ca、Sr或Ba的乙酸盐,最优选为乙酸锶。
掺杂氧化铝(其为煅烧之后的掺杂氧化铝)所包含的稀土金属氧化物、碱土金属氧化物或它们的混合物的最大含量为至多20重量%,优选地最大含量小于12重量%,最优选地含量小于10重量%。将至少50重量%,优选至少大于90重量%,最优选100重量%的存在于氧化铝负载的钙钛矿型氧化物组合物中的稀土金属氧化物、碱土金属氧化物或它们的混合物以稀土金属盐、碱土金属盐或它们的混合物的形式添加到勃姆石悬浮液中。通过煅烧由盐形成氧化物。掺杂氧化铝在用浸渍水溶液浸渍掺杂氧化铝的步骤中提供均匀分散的成核位点,以便获得氧化铝负载的钙钛矿型氧化物组合物。
特别地,如果掺杂氧化铝(其为煅烧之后的掺杂氧化铝)包含氧化镧,则氧化镧的最大含量为至多20重量%,优选地最大含量小于12重量%,最优选地含量小于10重量%。通过煅烧由镧盐形成氧化镧。由于氧化镧的含量低,在氧化铝负载的钙钛矿型氧化物组合物中没有形成LaAlO3。
优选将勃姆石盐混合物喷雾干燥以形成干燥的勃姆石盐混合物。
优选地将干燥的勃姆石盐混合物在450℃至1200℃之间的温度,优选500℃至600℃之间的温度下煅烧至少0.5小时,更优选0.5至5小时的时间,以形成掺杂氧化铝。分别选择温度和时间。
可以通过本领域已知的任何浸渍方法,优选通过初湿浸渍法进行掺杂氧化铝的浸渍。这种方法通常如下设置:用浸渍水溶液浸渍掺杂氧化铝的在80%至100%之间的孔体积。
浸渍水溶液包含按照钙钛矿ABO3型氧化物分子式的特定化学计量比的水溶性盐的混合物。
浸渍水溶液的这些一种或多种水溶性盐优选为:稀土元素的乙酸盐或硝酸盐,优选原子序数在57至60之间的稀土元素的乙酸盐或硝酸盐,更优选La的乙酸盐或硝酸盐,碱土元素的乙酸盐或硝酸盐,优选Sr、Ba和Ca的乙酸盐或硝酸盐,更优选Sr的乙酸盐或硝酸盐,Pb2+和/或Bi3+的乙酸盐或硝酸盐,以及过渡金属的水溶性盐,该过渡金属的水溶性盐包括柠檬酸铁铵、乳酸钛铵、乙酸锆或它们的混合物。更优选地,水溶性盐为乙酸锆、柠檬酸铁铵和乳酸钛铵。
本发明的第一方面的步骤ii)如下设置:浸渍水溶液包含水溶性盐的混合物。水溶性盐可以包含a)、b)和c)中的至少一种与d)中的至少一种的混合物:
a)稀土元素的乙酸盐或硝酸盐,优选原子序数在57至60之间的稀土元素的乙酸盐或硝酸盐,更优选La的乙酸盐或硝酸盐,
b)碱土元素的乙酸盐或硝酸盐,优选Sr、Ba和Ca中的一种或多种的乙酸盐或硝酸盐,更优选Sr的乙酸盐或硝酸盐,
c)Pb2+和Bi3+的乙酸盐或硝酸盐中的一种或多种,以及
d)过渡金属的水溶性盐中的一种或多种,例如Fe、Ti和/或Zr的过渡金属盐,包括例如柠檬酸铁铵、乳酸钛铵、柠檬酸铁铵、乙酸锆或它们的混合物。
或者,浸渍水溶液可以仅包含一种水溶性盐,例如柠檬酸铁铵。
由于使用了掺杂氧化铝,因此优选仅施用一个浸渍步骤来获得这样的经浸渍的掺杂氧化铝,其具有通过浸渍获得高负载量的能力。
将经浸渍的掺杂氧化铝优选在500℃至1100℃之间的温度,最优选700℃至1000℃之间的温度下煅烧。煅烧可以进行至少0.5小时,更优选0.5至5小时之间,例如3小时的时间。分别选择温度和时间。由于在步骤ii)中实现了均匀分散的浸渍,所以获得了具有非常低的钙钛矿微晶尺寸的氧化铝负载的钙钛矿型氧化物组合物。
根据本发明的第二方面,提供了一种根据本发明的方法制备的氧化铝负载的钙钛矿型氧化物组合物。
根据本发明的第三方面,提供了一种氧化铝负载的钙钛矿型氧化物组合物复合材料,其包括以下特征:
i)至少50重量%,优选在75至95重量%之间的掺杂氧化铝;以及
ii)在5至50重量%之间,优选在5至25重量%之间的具有分子式I的钙钛矿型氧化物:
ABO3,(I)
其中:
A包括稀土元素、碱土元素、碱金属元素、Pb2+、Bi3+或它们的混合物;以及
B包括一种或多种过渡金属,其中包括过渡金属的混合物;
ABO3的优选特征在于:在850℃煅烧3小时后具有小于5nm的微晶尺寸,优选在4nm至5nm之间的微晶尺寸;在700℃煅烧4小时后具有小于2nm的微晶尺寸。
过渡型氧化铝的X射线衍射图包括在大约2θ=46°下的强反射。
加权强度比R(参见方程式1)为氧化铝载体上钙钛矿材料的结晶度的量度。
R=[(I32/I46)]/mp(方程式1)
I32:在约32°下的反射强度
I46:在约46°下的反射强度
mP:钙钛矿质量/(钙钛矿质量(以ABO3计算)+氧化铝质量)。
如根据本发明的第一方面限定并制备掺杂氧化铝。氧化铝负载的钙钛矿型氧化物组合物优选包含至少80重量%的掺杂氧化铝。
优选地,根据分子式I的钙钛矿型氧化物的A包括碱土元素(更优选Sr、Ba或Ca中的至少一种)与稀土元素(更优选原子序数在57至60之间的元素)的混合物。最优选地,A包括Sr和La的混合物。
优选地,根据分子式I的钙钛矿型氧化物的B包括两种不同过渡金属的混合物,优选Fe与元素周期表的IVa族中的至少一种元素的混合物。更优选地,B包括Fe、Ti和Zr的混合物。
分别选择组分A和B,使得实现与三个氧化物阴离子的电荷平衡,因此各个组分的经摩尔比例加权的氧化态的总和等于+6。
钙钛矿型氧化物优选均匀地分散在氧化铝基质中,其中两者形成氧化铝负载的钙钛矿型氧化物组合物。不被理论限制,申请人认为钙钛矿型氧化物小晶体的均匀分散使得氧化铝基质能够充当扩散屏障,从而引起氧化铝负载的钙钛矿型氧化物复合材料的有益性能。
氧化铝负载的钙钛矿型氧化物组合物可以具有在50m2/g至300m2/g之间,优选在100m2/g至200m2/g之间的BET比表面积,以及在0.1ml/g至1.5ml/g之间,优选在0.5ml/g至1.0ml/g之间的孔体积。
附图说明
现在将参考以下非限制性的实施例和附图来描述本发明,其中:
图1表示实施例1的在700℃煅烧4小时之后以及在850℃煅烧3小时之后的X射线衍射图,其中标记有星号(*)的反射示出钙钛矿型氧化物的X射线图的反射;
图2表示实施例2的在700℃煅烧4小时之后以及在850℃煅烧3小时之后的X射线衍射图,其中标记有星号(*)的反射示出钙钛矿型氧化物的X射线图的反射;
图3表示实施例2和比较例1的在700℃煅烧4小时之后以及在850℃煅烧3小时之后的X射线衍射图;
图4表示实施例2和比较例2的在700℃煅烧4小时之后以及在850℃煅烧3小时之后的X射线衍射图,其中标记有星号(*)的反射示出钙钛矿型氧化物的X射线图的反射,标记有井号(#)的反射示出SrAl2O4的X射线图的反射,标记有加号(+)的反射示出SrCO3的X射线图的反射;
图5表示实施例3和比较例3的在700℃煅烧4小时之后的X射线衍射图,其中标记有星号(*)的反射示出钙钛矿型氧化物的X射线图。
具体实施方式
通过以下方式测量均匀性:扫描电子显微镜(SEM)横截面成像,任选地连同EDX(能量扩散X射线分析)元素映射,它们揭示掺杂氧化铝和钙钛矿型氧化物的域尺寸。
通过使用分析(022)-反射(在空间群Fm-3c中)的Debye-Scherrer方法来确定钙钛矿型氧化物的晶体尺寸。在850℃煅烧3小时之后确定的是其小于5nm,在700℃煅烧3小时之后确定的是其小于2nm。
通过在液氮温度下使用典型的体积装置(如来自Quantachrome的Quadrasorb)进行N2物理吸附来测量比表面积和孔体积。使用BET理论(DIN ISO 9277)确定比表面积,而根据DIN 66131确定孔体积。
实施例
实施例1-具有20重量%的钙钛矿La0,5Sr0,5Fe0,5Ti0,5O3的复合材料
通过将乙酸镧水溶液与5重量%勃姆石的水悬浮液混合来制备含有10重量%La2O3的γ氧化铝。随后将混合物喷雾干燥并在500℃下煅烧1小时。
通过初湿浸渍法,用乙酸锶、柠檬酸铁铵和Tyzor LA(钛溶液)的混合溶液浸渍La掺杂的氧化铝,以实现在煅烧之后4.8重量%SrO、3.8重量%Fe2O3和3.8重量%TiO2的负载量。将产物分别在850℃煅烧3小时以及在700℃煅烧4小时。
图1示出在850℃煅烧3小时以及在700℃煅烧4小时之后通过实施例1获得的材料的X射线衍射图。
实施例2-具有20重量%的钙钛矿La0,5Sr0,5Fe0,5Zr0,5O3的复合材料
通过将乙酸镧水溶液与5重量%勃姆石的水悬浮液混合来制备含有7.8重量%La2O3的γ氧化铝。随后将混合物喷雾干燥并在500℃下煅烧1小时。
通过初湿浸渍法,用柠檬酸铁铵、乙酸锆和乙酸锶的混合溶液浸渍掺杂氧化铝,以实现3.4重量%Fe2O3、5.3重量%ZrO2和4.4重量%SrO的负载量。将产物分别在850℃煅烧3小时以及在700℃煅烧4小时。
在图2中,示出了在850℃煅烧3小时以及在700℃煅烧4小时之后获得的材料的X射线衍射图。
比较例1-具有20重量%的钙钛矿La0,5Sr0,5Fe0,5Ti0,5O3的复合材料
根据US 4921829的实施例5制备复合材料。
首先通过将100.9g的γ氧化铝添加到400ml的具有425g六水合硝酸镧的水溶液中来合成LaAlO3粉末。将所得混合物进行蒸发并干燥。之后,在空气中将混合物在600℃煅烧3小时,再在900℃煅烧8小时以获得LaAlO3粉末。
在第二步骤中,将LaAlO3粉末与一定量的镧、锶、铁和锆的硝酸盐水溶液混合,所述一定量使得在经煅烧的复合材料中实现3.4重量%Fe2O3、5.3重量%ZrO2、4.4重量%SrO和额外的6.9重量%La2O3的负载量。在空气中将所得混合物在110℃干燥10小时,而后分别在700℃煅烧4小时以及在850℃煅烧3小时。
在图3中,示出了在850℃煅烧3小时以及在700℃煅烧4小时之后获得的材料的X射线衍射图。
结果表明,所得产物与本发明的组合物的不同之处在于,不存在氧化铝,钙钛矿晶体尺寸更高,比表面积明显更低。
比较例2-具有20重量%的钙钛矿La0,5Sr0,5Fe0,5Ti0,5O3的复合材料
根据US 5882616的实施例6制备复合材料。
将25g的γ-氧化铝珠粒用含有一定量的镧、锶、铁和锆的硝酸盐、5g乙醇和10g柠檬酸的水溶液浸渍两次,所述一定量使得在经煅烧的复合材料中实现6.9重量%La2O3、3.4重量%Fe2O3、5.3重量%ZrO2和4.4重量%SrO的负载量。在第一次浸渍后将所得材料在真空下干燥(以除去溶液)。在第二次浸渍后,将产物分别在700℃煅烧4小时以及在850℃煅烧3小时。
在图4中,示出了在850℃煅烧3小时以及在700℃煅烧4小时之后获得的材料的X射线衍射图。
粉末X射线衍射图揭示了与本发明的组合物显著不同的相。具体而言,锶不形成钙钛矿结构的一部分,而是在700℃煅烧后以SrCO3的形式存在,在850℃煅烧后以SrAl2O4的形式存在。因此,可以得出结论,该流程不适用于形成所需的组合物。结果包括在下表1中。
表1:
n.d.=未检测到,n.a.=不适用。
实施例3-具有10重量%的钙钛矿LaFeO3的复合材料
通过将乙酸镧水溶液与5重量%勃姆石的水悬浮液混合来制备含有11.7重量%La2O3的γ氧化铝。随后将混合物喷雾干燥并在500℃下煅烧1小时。
通过初湿浸渍法用柠檬酸铁铵的溶液浸渍掺杂氧化铝,以实现3.3重量%Fe2O3的负载量。将产物分别在850℃煅烧3小时以及在700℃煅烧4小时。
在图5中,示出了在700℃煅烧4小时之后获得的材料的X射线衍射图。
比较例3-具有10重量%的钙钛矿LaFeO3的复合材料
根据US2012/0046163A1的实施例3制备复合材料。
将在75ml水中的2.2g乙酸铁与在75ml水中的4.46g乙酸镧的混合物混合,而后将该混合物添加到通过使27g镧掺杂的氧化铝(市售为PURALOX TH100/150L4)与150ml水混合而制得的分散体中。向该混合物中加入11.2g的25%NH3溶液以达到10的pH值。在搅拌1.5小时之后,过滤沉淀物并将得到的粉末在700℃煅烧4小时。
在图5中,示出了在700℃煅烧4小时之后获得的材料的X射线衍射图。
对根据实施例3和比较例3的材料的X射线衍射图的比较清楚地表明了钙钛矿相的结晶度的差异。
如图2中的星号所示,对于比较例3,可以检测到结晶钙钛矿相,然而钙钛矿反射非常弱。因此,可以得出结论,钙钛矿相以几乎X射线无定形的状态存在。
结果包括在下表2中。
表2:
Claims (16)
1.一种制备氧化铝负载的钙钛矿型氧化物组合物的方法,所述方法包括以下步骤:
i)提供掺杂氧化铝,所述掺杂氧化铝包含:
a.氧化铝和稀土金属氧化物,或
b.氧化铝和碱土金属氧化物,或
c.氧化铝以及稀土金属氧化物和碱土金属氧化物的混合物,
其中通过包括至少以下步骤的方法提供所述掺杂氧化铝:
A)制备勃姆石悬浮液,所述勃姆石悬浮液包含勃姆石;
B)制备盐水溶液,所述盐水溶液包含:
a.稀土金属盐,或
b.碱土金属盐,或
c.稀土金属盐和碱土金属盐的混合物;
C)将所述勃姆石悬浮液与所述盐水溶液相结合以形成勃姆石盐混合物;
D)干燥勃姆石盐混合物以形成干燥的勃姆石盐混合物;以及
E)煅烧干燥的勃姆石盐混合物以形成掺杂氧化铝;
ii)用浸渍水溶液浸渍掺杂氧化铝以形成经浸渍的掺杂氧化铝,所述浸渍水溶液包含以下的一种或混合物:水溶性稀土金属盐、水溶性碱土金属盐、水溶性碱金属盐、水溶性Pb2+盐、水溶性Bi3+盐和水溶性过渡金属盐;以及
iii)煅烧经浸渍的掺杂氧化铝。
2.根据权利要求1所述的方法,其中,勃姆石悬浮液进一步包含二氧化硅、二氧化钛、碱土金属的水溶性盐、稀土金属的水溶性盐、锆的水溶性盐、或者它们的混合物。
3.根据权利要求1或权利要求2所述的方法,其中,盐水溶液至少包含水、以及水溶性稀土金属盐、水溶性碱土金属盐或它们的混合物。
4.根据权利要求1至3中任一项所述的方法,其中,浸渍掺杂氧化铝包括初湿浸渍法。
5.根据权利要求1至4中任一项所述的方法,其中,用浸渍水溶液浸渍掺杂氧化铝的在80%至100%之间的孔体积。
6.根据权利要求1至5中任一项所述的方法,其中,水溶性盐包含a)、b)和c)中的至少一种与d)中的至少一种的混合物:
a)稀土元素的乙酸盐或硝酸盐,优选原子序数在57至60之间的稀土元素的乙酸盐或硝酸盐,更优选La的乙酸盐或硝酸盐,
b)碱土元素的乙酸盐或硝酸盐,优选Sr、Ba和Ca中的一种或多种的乙酸盐或硝酸盐,更优选Sr的乙酸盐或硝酸盐,
c)Pb2+和Bi3+的乙酸盐或硝酸盐中的一种或多种,以及
d)包括以下的过渡金属的水溶性盐中的一种或多种:柠檬酸铁铵、乳酸钛铵、乙酸锆或它们的混合物。
7.根据权利要求1至6中任一项所述的方法,其中,将经浸渍的掺杂氧化铝在500℃至1100℃之间的温度,优选700℃至1000℃之间的温度下煅烧,各煅烧进行至少0.5小时的时间,更优选0.5至5小时之间的时间。
8.一种根据权利要求1至7中任一项所述的方法制备的氧化铝负载的钙钛矿型氧化物组合物。
9.一种氧化铝负载的钙钛矿型氧化物组合物复合材料,其包括以下特征:
i)至少50重量%的掺杂氧化铝;以及
ii)在5至50重量%之间的具有以下分子式的钙钛矿型氧化物:
ABO3,
其中:
A包括稀土元素、碱土元素、碱金属元素、Pb2+、Bi3+或它们的混合物,以及
B包括过渡金属,其中包括过渡金属的混合物;以及
ABO3的特征在于:在850℃煅烧3小时后具有小于5nm的微晶尺寸;在700℃煅烧4小时后具有小于2nm的微晶尺寸。
11.根据权利要求8至10中任一项所述的氧化铝负载的钙钛矿型氧化物组合物,其中,A包括一种碱土元素和一种稀土元素的混合物,所述碱土元素优选为Sr、Ba、Ca中的一种或多种,所述稀土元素更优选为原子序数在57至60之间的元素。
12.根据权利要求8至11中任一项所述的氧化铝负载的钙钛矿型氧化物组合物,其中,B包括两种不同过渡金属的混合物,优选Fe与元素周期表的IVa族中的元素的混合物。
13.根据权利要求8至12中任一项所述的氧化铝负载的钙钛矿型氧化物组合物,其特征还在于,所述氧化铝负载的钙钛矿型氧化物组合物包括在50至300m2/g之间,优选在100至200m2/g之间的比表面积,以及在0.1至1.5ml/g之间,优选在0.5至1.0ml/g之间的孔体积。
14.根据权利要求8至13中任一项所述的氧化铝负载的钙钛矿型氧化物组合物,其能够根据权利要求1至7中任一项所述的方法获得。
15.根据权利要求8至14中任一项所述的氧化铝负载的钙钛矿型氧化物组合物,其中所述掺杂氧化铝不包括LaAlO3。
16.根据权利要求8至14中任一项所述的氧化铝负载的钙钛矿型氧化物组合物在用于排放控制应用的催化体系中的用途,特别是在NOx捕获催化剂中的用途。
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US5882616A (en) * | 1995-06-07 | 1999-03-16 | Megtec Systems, Inc. | Catalyst and method for oxidizing oxygen-containing organic compounds in waste gas |
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US5882616A (en) * | 1995-06-07 | 1999-03-16 | Megtec Systems, Inc. | Catalyst and method for oxidizing oxygen-containing organic compounds in waste gas |
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