CN102639461B - 钛酸铝多孔结构 - Google Patents

钛酸铝多孔结构 Download PDF

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Publication number
CN102639461B
CN102639461B CN201080042278.5A CN201080042278A CN102639461B CN 102639461 B CN102639461 B CN 102639461B CN 201080042278 A CN201080042278 A CN 201080042278A CN 102639461 B CN102639461 B CN 102639461B
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oxide
loose structure
zro
composition
hfo
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CN102639461A (zh
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S·拉菲
N·纳哈斯
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Abstract

本发明涉及包含陶瓷材料的多孔结构，该陶瓷材料主要包含氧化物材料或由其构成，所述氧化物材料包含对应于以下组成的钛、铝、锆和硅，以基于氧化物的重量%计：大于15%并低于55%的Al2O3；大于20%并低于45%的TiO2；大于1%并低于30%的SiO2；总计大于0.7%并低于20%的至少一种选自ZrO2，Ce2O3和HfO2的氧化物；低于1%的MgO；所述组成进一步包含其它元素，基于氧化物，其选自CaO、Na2O、K2O、SrO、B2O3和BaO，所述氧化物的总和量低于15%并大于1%，所述材料通过所述简单氧化物或它们的前体之一的反应烧结获得，或通过对应于所述组成的烧结颗粒的热处理获得。

Description

钛酸铝多孔结构
本发明涉及多孔结构，如催化剂载体或者颗粒过滤器，其构成过滤和/或活性部分的材料基于钛酸铝。形成根据本发明的载体或陶瓷过滤器的基础的陶瓷材料或者主要由元素Al、Ti的氧化物构成。所述多孔结构最通常是蜂窝状结构并且特别地用于柴油类型内燃机的排气管道中，其性能得到改善。
在本说明书的后面部分中，为了方便起见并且根据在陶瓷领域的习惯，将通过参考相应的简单氧化物(例如Al2O3或TiO2)描述所述包含所述元素的氧化物。特别地，在下面说明书中，除非另外提到，所述构成根据本发明的氧化物的不同元素的比例通过参考相应简单的氧化物的重量以相对于在所描述化学组成中存在的氧化物的总量的重量百分比给出。
在本说明书的剩余部分中，将描述在可以除去在来自汽油或者柴油内燃机的废气中包含的污染物的过滤器或者催化剂载体的特定领域(本发明涉及的领域)中的应用和优点。目前，所有用于净化废气的结构通常都具有蜂窝状结构。
据已知，在它的使用期间，颗粒过滤器经受一系列的过滤(烟灰积累)和再生(烟灰去除)阶段。在过滤阶段期间，由发动机排出的烟灰颗粒被保留和沉积在过滤器内部。在再生阶段期间，烟灰颗粒在过滤器内部被烧掉以便恢复其过滤性能。因此将理解的是，构成过滤器的材料在低温和高温时的机械强度性质对于这种应用是极其重要的。
目前，过滤器主要地由多孔陶瓷材料制成，最通常地由金刚砂或者堇青石制成。这种类型的金刚砂催化过滤器例如描述在专利申请EP816065、EP1142619、EP1455923或者WO2004/090294和WO2004/065088中。这种过滤器可以获得具有优异的热导率和具有孔隙度特征(特别地平均孔径和孔径分布)的化学上惰性的过滤结构，其对于过滤由内燃机产生的烟灰的应用是理想的。
然而，仍然存在一些这种材料特有的缺点：
第一个缺点与SiC的稍微高的热膨胀系数(大于3×10-6K-1)有关，这不允许制备大尺寸的整料过滤器并且最经常必须将该过滤器分割成多个使用胶合剂结合在一起的蜂窝状元件，如在专利申请EP1455923中描述的那样。经济性的第二个缺点与极其高的允许烧结(以确保该蜂窝状结构的足够的热机械强度)的烧制温度(典型地高于2100℃)有关，特别地在过滤器的连续再生阶段期间更如此。这种温度要求安装特殊设备，这显著地提高了最后获得的过滤器的成本。
另一方面，虽然由堇青石制成的过滤器是已知的并且使用很长时间了(由于它们的低成本)，然而目前已知的是，在这种结构中可能遇到问题，特别地在控制不良的再生循环期间，在其期间，过滤器可能局部地经受高于堇青石的熔点的温度。这些热点的后果可为从过滤器的效率的部分损失至在最严重的情况下它完全的破坏。而且，堇青石不具有足够的化学惰性(考虑连续的再生循环期间达到的温度)，并因此它易于反应并被来源于在该过滤阶段期间已经积累在该结构中的润滑剂、燃料或其它油的残余物的物类腐蚀，该现象还可以是该结构的性能快速退化的原因。
例如，这种缺点已经描述在专利申请WO2004/011124中，其提出用多铝红柱石(10-40重量%)增强的基于钛酸铝(60-90重量%)的过滤器以克服它们，其耐用性得到改善。
根据另一实施方案，专利申请EP1559696提出使用粉末以制备通过在1000-1700℃使铝、钛和镁的氧化物反应性烧结获得的蜂窝式过滤器。在烧结之后获得的材料呈两种相的混合物形式：假板钛矿Al2TiO5结构类型的主相，其包含钛、铝和镁，和NayK1-yAlSi3O8类型的长石次相。
本发明的目的因此是提供多孔结构，其包含基于氧化物的替代材料，尤其在热膨胀系数、孔隙度和机械强度方面具有改善的性能，以使得使得它们更有利地用于制备过滤和/或催化多孔结构，典型地蜂窝状结构。
在机械强度和孔隙度之间的折衷通过特征值MOR×PO(在压缩断裂模量(modulederuptureencompression)乘开口孔隙体积)进行评价，较高的值体现在孔隙度性质和机械强度性质之间较好的折衷。
更确切地说，本发明涉及包含陶瓷材料的多孔结构，该陶瓷材料的化学组成包含，以基于氧化物的重量%计：
-大于15%并低于55%的Al2O3；
-大于20%并低于45%的TiO2；
-大于3.5%并低于30%的SiO2；
-总计大于0.7%并低于20%的至少一种选自ZrO2、Ce2O3、HfO2的氧化物；
-低于1%的MgO；
-低于0.7%的Fe2O3；
所述组成进一步包含其它元素，基于氧化物，其选自CaO、Na2O、K2O、SrO、B2O3、BaO，所述氧化物的总和量低于15%并大于1%，所述材料通过所述简单氧化物或它们的前体之一的反应性烧结获得，或通过满足所述组成的烧结颗粒的热处理获得。
优选地，该多孔结构由所述陶瓷材料构成。
优选地，Al2O3占该化学组成的大于20%，所述百分比以基于对应于存在的元素的氧化物的重量计给出。例如，特别地对于过滤器或者催化载体类型的应用，Al2O3可以占该化学组成的大于25%，更优选地大于35%。优选地，Al2O3占该化学组成的低于54%甚至低于53%，所述百分比以基于氧化物按重量计给出。
优选地，当SiO2占该化学组成的大于10%，Al2O3占该化学组成的低于52%，甚至低于51%，所述百分比基于氧化物以重量计给出。
优选地，TiO2占该化学组成的大于22%，非常优选地大于25%。优选地，TiO2占该化学组成的低于43%，甚至低于40%，非常优选地低于38%，所述百分比以基于氧化物按重量计给出。
优选地，SiO2占该化学组成的大于2%，甚至多于3%，甚至多于3.5%。优选地，SiO2占该化学组成的低于25%非常优选地低于20%，百分比以基于氧化物的重量计给出。
优选地，氧化物ZrO2和/或Ce2O3和/或HfO2它们全部占该化学组成的大于0.8%，非常优选地大于1%，甚至大于2%，所述百分比基于氧化物以重量计给出。优选地，所述氧化物ZrO2和/或Ce2O3和/或HfO2总计占该化学组成的低于10%，非常优选地低于8%。根据一个可能的实施方案，该组成仅仅包含如上所述比例的氧化锆。
在上面给出的组成中，根据本发明的另一种可能并且优选的实施方案，ZrO2因此可以相同比例用ZrO2和Ce2O3的组合代替，只要ZrO2含量保持大于0.7%，甚至大于0.8%，甚至大于1%。例如，在这种情况下，所述材料包含大于0.8重量%并低于10重量%，非常优选地低于8重量%的(ZrO2+Ce2O3)，其中(ZrO2+Ce2O3)是在所述组成中的两种氧化物的重量含量的总量。
当然，在本说明书的背景中，然而该组成可能地包括其它不可避免杂质的形式的化合物。特别地，甚至当最初将仅仅一种包含锆的反应剂引入到制备根据本发明的结构的方法中时，众所周知所述反应剂最通常包括不可避免杂质形式的少量铪，其有时可以最高至该引入的锆的总量的1mol%或2mol%。
优选地，MgO占该化学组成的低于0.9%，甚至低于0.5%，甚至低于0.1%，基于氧化物以重量计。
该多孔结构还包含其它元素，如硼，Ca、Sr、Na、K、Ba类型的碱金属或碱土金属，所述元素的总和量优选地按重量计低于15%，例如按重量计低于13%，甚至12%(基于相应的氧化物B2O3、CaO、SrO、Na2O、K2O、BaO)，相对于所有在所述多孔结构中存在的元素的对应氧化物的重量含量。所述氧化物的总和量可以占该化学组成的大于1%，甚至大于2%，甚至大于4%，甚至大于5%，甚至大于6%。
优选地，在根据本发明的结构的组成中，为了获得较高的孔隙度，有必要限制Na和K物类的浓度。特别地根据本发明的优选实施方案，在构成该结构的氧化物材料中的组成中的氧化物Na2O和K2O的总量优选地低于1重量%。
根据本发明的化学组成还可以包括其它微量元素。
该化学组成实际上可以包括其它元素，如Co、Fe、Cr、Mn、La、Y、Ga，基于相应的氧化物CoO、Fe2O3、Cr2O3、MnO2、La2O3、Y2O3、Ga2O3，存在的所述元素的总和量优选地低于2重量%，例如低于1.5重量%，甚至低于1.2重量%，相对于在所述组成中的所有氧化物的重量。每种微量元素的重量百分比，基于对应氧化物的重量，优选地低于0.7%，甚至低于0.6%，甚至低于0.5%。
为了避免不必要地增加本说明书的负担，如上所述地，在根据本发明的材料的组成的各种优选的实施方案之间的所有根据本发明的可能组合将不再报道。然而，显然的是，在本说明书的范围内可以设想上面描述的初始的和/或优选的值和范围的所有可能的组合，并且它们应该被认为是由本申请人在本说明书的范围内进行了描述(特别地两、三种或更多种组合)。
根据本发明的多孔结构还可以主要地包含或由钛酸铝类型的氧化物相、至少一个含硅酸盐的相和基本上由二氧化钛TiO2和/或氧化锆ZrO2和/或二氧化铈CeO2和/或二氧化铪HfO2组成的相构成。
所述一个或多个含硅酸盐的相的比例可以为该材料的总重量的5-50%，优选地8-45%，非常优选地该材料总重量的10-40%。根据本发明，所述一个或多个含硅酸盐的相可以主要由二氧化硅和氧化铝组成。优选地，在所述一个或多个含硅酸盐的相中的二氧化硅的比例大于30%，甚至大于35%。
最特别地，根据本发明的多孔结构可以有利地包含钛酸铝类型的主要氧化物相并且具有下列组成，基于氧化物以重量百分比计：
-大于35%并低于53%的Al2O3；
-大于25%并低于40%的TiO2；
-大于2%并低于20%的SiO2；
-大于1%并低于5%的ZrO2；
-低于1%的MgO；
-低于0.7%的Fe2O3；
-总计大于2%并低于13%的至少一种选自CaO、Na2O、K2O、SrO、B2O3、BaO的氧化物。
构成根据本发明的多孔结构的材料可以通过任何通常用于本领域中的技术获得。
根据第一种变型，构成该结构的材料可以直接地，以常规方式，通过以适当的比例简单混合初始反应剂(以获得希望的组成)，然后通过加热和固体状态反应(反应性烧结)获得。
所述反应剂可以是简单的氧化物(例如Al2O3、TiO2)，和任选地可进入该结构中的元素的其它氧化物，例如呈固溶体形式。根据本发明还可以使用所述氧化物的任何前体，例如呈以上元素的碳酸盐、氢氧化物或者其它有机金属形式。术语“前体”理解为在通常在热处理之前的阶段，即在一般地低于1000℃，甚至低于800℃甚至低于500℃的加热温度下，其分解成相应的简单氧化物的材料。
根据另一种制备根据本发明的结构的方法，所述反应剂是对应于如上所述的化学组成的并由所述简单氧化物获得的烧结颗粒。预烧结所述初始反应剂的混合物，即它被加热至可以允许简单氧化物反应以形成包含至少一种钛酸铝类型的结构的主相的烧结颗粒的温度。根据这种实施方案还可以使用上述的氧化物的前体。完全如同上述，烧结所述前体的混合物，即它被加热至可以使前体反应以便形成至少主要地包含钛酸铝类型结构的相的烧结颗粒的温度，然后研磨以获得初始反应剂。
一种用于制备这种根据本发明的结构的方法通常为以下：
首先，将初始反应剂以适当的比例混合以获得希望的组成。
以在本领域中熟知的方式，该制备方法一般地包括使反应剂的初始混合物与甲基纤维素类型的有机粘结剂和致孔剂(例如，淀粉、石墨、聚乙烯、PMMA等等类型)混合的步骤，并且逐渐加入水直至获得可以进行挤出蜂窝状结构的步骤所需要的可塑性。
例如，在第一步期间，使初始混合物与1-30质量%的至少一种根据所希望的孔径选择的致孔剂混合，然后加入至少一种有机增塑剂和/或有机粘结剂和水。
该混合产生呈糊状物形式的均质产品。使用熟知的技术，使该产品挤出通过具有适当形状的模具的步骤可以获得蜂窝状整料。该方法然后例如可以包括干燥该获得的整料的步骤。在干燥步骤期间，获得的粗制陶瓷整料一般地通过微波干燥或者通过在足够的温度下干燥足够的时间，该温度和时间使得非化学结合水的含量为低于1质量%。在希望获得颗粒过滤器的情况下，该方法可以进一步地包括在该整料的每一端使每两个通道中一个通道阻塞的步骤。
烧制该整料(其过滤部分基于钛酸铝)的步骤原则上在高于1300℃而不超过1800℃，优选地不超过1750℃的温度下进行。该温度特别地根据存在于多孔材料中的其它相和/或氧化物进行调节。最通常，在该烧制步骤期间，整料结构在包含氧或者中性气体的气氛中被加热至1300℃-1600℃的温度。
虽然本发明的优点之一在于获得其尺寸可被大大提高的整料结构而不需要分割的可能性，与SiC过滤器(如上所述)不同，根据一个的实施方案(其然而不是优选的)，该方法可以任选地包括使用熟知的技术(例如在专利申请EP816065中描述的那些技术)将整料装配为组装过滤结构的步骤。
由根据本发明的多孔陶瓷材料制成的催化剂载体或者过滤结构优选地是蜂窝状类型的并具有大于10%的合适孔隙度同时中心在5-60微米的孔径，特别地20-70%，优选地30-60%，平均孔径理想地为10-20微米，其通过水银孔率测量法使用Micromeritics9500型设备测量。
这种过滤结构一般地具有包含一组通过由多孔材料形成的壁分隔的具有互相平行轴的相邻孔道或者通道的中央部分。
在颗粒过滤器中，所述孔道通过塞子在它们的一端或另一端被阻塞以便界定朝着进气口面开口的进气腔室和朝着气体排出面开口的出口腔室，使得该气体穿过该多孔壁。
本发明还涉及从如上面所述的结构并通过沉积(优选地通过浸渍)至少一个负载的或者优选地非负载的活性催化相而获得的过滤器或者催化剂载体，该活性催化相一般地包含至少一种贵金属，如Pt和/或Rh和/或Pd和任选的氧化物如CeO2、ZrO2、CeO2-ZrO2。该催化剂载体还具有蜂窝状结构，但是所述孔道不用塞子阻塞和该催化剂被沉积在该通道的孔隙中。
本发明和它的优点通过阅读以下非限制性实施例而更好地理解。在这些实施例中，除非另作说明，否则所有的百分比含量以重量计给出。
实施例
在实施例中，从以下原材料制备样品：
-AlmatisCL4400FG氧化铝，其包含99.8%Al2O3的氧化铝并且具有约5.2微米的中值粒径d50；
-TRONOXT-R二氧化钛，其包含99.5%TiO2并且具有约0.3微米的直径；
-ElkemMicrosiliciaGrade971USiO2，具有99.7%的纯度；
-包含约97%CaO的石灰，其中大于80%的颗粒具有低于80微米的直径；
-包含大于98.5%SrCO3的碳酸锶，其由SociétédesProduitsChimiquesHarbonnières销售；
-具有大于98.5%纯度和中值粒径d50=3.5微米的氧化锆，其以商标CC10由Saint-GobainZirPro公司销售。
根据本发明的样品和对比样品从以适当的比例混合的前述反应剂获得。
更确切地说，使初始反应剂的共混物混合然后压制为圆柱形，其然后在表1中指出的温度在空气中在1450℃(实施例1的系列)或在1500℃(实施例2的系列)烧结4小时。如此获得以下实施例的材料或样品。
然后分析该制备的样品。对每个实施例样品进行的分析的结果在表1中给出。
在表1中：
1)化学组成(以基于氧化物的重量%表示)通过X射线荧光进行测定；
2)在耐火产品中存在的结晶相通过X射线衍射和微探针分析EPMA(电子探针微分析器)进行表征。基于如此获得的结果，能够估算每个相的重量百分比和它的组成。在表1中，AT指示氧化物Al2O3和TiO2的固溶体(主相)，PS指示存在含硅酸盐的相，其它一个或多个相指示存在至少一个其它次相P2和"~"表示该相以微量形式存在；
3)抗压机械强度(R)在室温下在配备有10kN传送器(capteur)的LLOYD压机上通过以1mm/min的速度压缩该制备的样品进行测定；和
4)密度通过阿基米德方法常规技术进行测量。在表1中给出的孔隙度对应于在理论密度(在没有孔隙的情况下该材料的期望的最大密度并且通过对该研磨产品的氦比重法(picnométriehélium)进行测量)和测量密度之间的差值，其以百分比给出。
表1
对比实施例1和2涉及不根据本发明的结构，其中它们包含过低的锆或锶浓度。从表1的数据可见孔隙度和机械强度的结合特征得到改善：对于相同的烧结或烧制温度，可见根据本发明的实施例的孔隙度与对比实施例的孔隙度是可相比的。同时，如在表1中指示，根据本发明的实施例具有比对比实施例显著更高的强度R。
通过比较上述数据，可见根据本发明获得的多孔结构显示出在机械强度和孔隙度之间显著改善的折衷。绝对性地，因此观察到反映在机械强度和孔隙度之间折衷的积MOR×PO(压缩断裂模量乘开口孔隙体积)对于根据本发明的多孔体是系统地更高的(对于相同的烧结温度)。因此，与对比实施例1(低于0.7%的ZrO2含量)和1a(低于1%的CaO、Na2O、K2O、SrO、B2O3、BaO含量)相比较，实施例1和1a(其对应于根据在本文中附带的主要权利要求的组成并且包含大于3.5%的SiO2和总计大于1%氧化物CaO、Na2O、K2O、SrO、B2O3、BaO)显示出最好的折衷。
因此，本发明的产品根据以下需要使得可以：
-在施加的烧制温度下获得较好的与该材料的希望组成有关的性质；或
-调节该材料的高孔隙度水平(特别地通过向初始反应剂加入致孔剂)同时维持优良的机械稳定性。

Claims (15)

1.包含陶瓷材料的多孔结构，该陶瓷材料的化学组成包含以下成分，以基于氧化物的重量%计：
-大于15%并低于55%的Al2O3；
-大于20%并低于45%的TiO2；
-大于3.5%并低于30%的SiO2；
-总计大于0.7%并低于20%的至少一种选自ZrO2、Ce2O3、HfO2的氧化物；
-低于1%的MgO；
-低于0.7%的Fe2O3；
-其它氧化物，其选自CaO、Na2O、K2O、SrO、B2O3、BaO，所述其它氧化物的总和量低于15%并大于1%，和
所述材料通过所述氧化物或它们的前体之一的反应性烧结获得，或通过满足所述组成的烧结颗粒的热处理获得，和
其中所述多孔结构由下列相构成：钛酸铝氧化物相、至少一个主要由二氧化硅和氧化铝组成的含硅酸盐相和基本上由二氧化钛TiO2和/或氧化锆ZrO2和/或二氧化铈CeO2和/或二氧化铪HfO2组成的相。
2.根据权利要求1的多孔结构，其中所述组成包含总计大于0.8%的至少一种选自ZrO2、Ce2O3、HfO2的氧化物。
3.根据权利要求1-2之一的多孔结构，其中所述选自ZrO2、Ce2O3、HfO2的氧化物是ZrO2。
4.根据权利要求1-2之一的多孔结构，其中所述选自ZrO2、Ce2O3、HfO2的氧化物是ZrO2和Ce2O3，ZrO2含量大于0.7%。
5.根据权利要求1-2之一的多孔结构，其中所述组成包含低于54%的Al2O3。
6.根据权利要求1-2之一的多孔结构，其中所述组成包含大于22%的TiO2。
7.根据权利要求1-2之一的多孔结构，其中所述组成包含低于43%的TiO2。
8.根据权利要求1-2之一的多孔结构，其中所述组成包含低于25%的SiO2。
9.根据权利要求1-2之一的多孔结构，其中所述组成包含低于0.5%的MgO。
10.根据权利要求1-2之一的多孔结构，其中所述组成包含总计低于10%的至少一种选自ZrO2、Ce2O3、HfO2的氧化物。
11.根据权利要求1-2之一的多孔结构，其中氧化物CaO、Na2O、K2O、SrO、B2O3、BaO的总和量低于13%。
12.根据权利要求1-2之一的多孔结构，其中氧化物CaO、Na2O、K2O、SrO、B2O3、BaO的总和量高于2%。
13.根据权利要求1-2之一的多孔结构，其中在构成该结构的氧化物材料的组成中的氧化物Na2O和K2O的总和量低于1%。
14.根据权利要求13的多孔结构，其中所述至少一个含硅酸盐相占该陶瓷材料的总重量的5-50%。
15.根据权利要求1-2之一的多孔结构，其具有蜂窝状类型的结构，该陶瓷材料构成所述结构，该结构具有大于10%的孔隙度和中心在5-60微米的孔径。
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