CN112423881A - 具有改善的耐热性的沸石以及使用该沸石的催化剂复合物 - Google Patents

具有改善的耐热性的沸石以及使用该沸石的催化剂复合物 Download PDF

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CN112423881A
CN112423881A CN201980034389.2A CN201980034389A CN112423881A CN 112423881 A CN112423881 A CN 112423881A CN 201980034389 A CN201980034389 A CN 201980034389A CN 112423881 A CN112423881 A CN 112423881A
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zeolite
catalyst
reformed
catalyst article
alumina
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纳容亚娜·饶·科玛泰帝
金恩锡
金永苏
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Heesung Catalysts Corp
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Abstract

本发明提供了一种重整沸石以及一种使用所述重整沸石的催化剂复合物，所述催化剂复合物具有改善的耐热性，并且用在以氨气或尿素作为还原剂的选择性催化还原(SCR)催化剂中，用在过滤器涂覆有所述SCR催化剂的过滤型选择性催化还原(SDPF)催化剂中，或者用在稀薄氮氧化物柴油氧化催化剂(NA‑DOC)中。在所述重整沸石和所述催化剂复合物中，作为沸石涂覆材料的氧化铝组分改善沸石的耐热性并提升高温条件下的催化效率。

Description

具有改善的耐热性的沸石以及使用该沸石的催化剂复合物
技术领域
本发明涉及一种重整沸石以及一种使用该重整沸石的催化剂复合物，该重整沸石和该催化剂复合物具有改善的耐热性，并且用在以氨气或尿素作为还原剂的选择性催化还原(SCR)催化剂中，或者用在过滤器涂覆有SCR催化剂的过滤型SCR催化剂中，或者用在稀薄氮氧化物柴油氧化催化剂中。根据本发明的重整沸石通过用氧化铝溶胶涂覆沸石或混合两者来制备。对于包含根据本发明的重整沸石的催化剂而言，可改善其在高温区域降低氮氧化物(NOx)的性能，并且可改善其即使在暴露于从内燃机等排放的高温废气时的热耐久性。
背景技术
在所使用的空气多于按化学计量燃烧所需的空气量的燃烧条件(即，在贫燃条件下运行的内燃机的燃烧条件)下，去除废气中的氮氧化物(NOx)是尤其困难的。
使用氨气的选择性催化还原(SCR)是一种施加至贫燃条件固定污染源用以降低NOx的可靠技术。在这项技术中，NOx在SCR催化剂的表面与充当还原剂的氨气发生反应，其因被还原成氮气(N2)而含量降低。一般来讲，将钒钛氧化物用作在300至450℃范围内的氮氧化物降低效率为90％或以上的选择性催化还原(SCR)的催化剂。ZSM5型沸石催化剂，Beta型沸石催化剂，和/或Fe或Cu等过渡金属的离子被交换的Fe-Beta、Cu-Beta、Fe-ZSM5和Cu-ZSM5型沸石催化剂被开发并用于需要高热耐久性(600℃或更高)和高活性温度范围(350至550℃)的应用。然而，耐热性问题依然存在。此类SCR也可被施加到过滤结构，并被称为SCRoF(过滤器上的SCR)或SDPF。在本发明中，将SCR称为过滤型SCR催化剂。同时，近期开发并应用了一种在柴油氧化催化剂(DOC)中包含NOx吸附材料的催化剂制品，用以改善低温活性，该催化剂制品被称为NA-DOC，在本发明中被称为NOx吸附型柴油氧化催化剂。在NOx吸附型柴油氧化催化剂或过滤型选择性催化还原催化剂中，需要提供如下这样的催化剂：该催化剂在暴露于从内燃机排放的高温废气时具有改善的高温活性和热耐久性，以及对有毒材料(诸如硫、磷、钙、锌和碱金属)具有抗毒性。
发明内容
技术问题
本发明通过将氧化铝溶胶施加到沸石以制备重整沸石并将重整沸石施加到NA-DOC、SCR或SDPF，来实现具有出色耐热性和高温活性的催化剂。
技术方案
本发明涉及一种催化剂制品。更具体地讲，该催化剂制品可为氮氧化物吸附型柴油氧化催化剂、选择性催化还原催化剂、或过滤型选择性催化还原催化剂，并且可包含置于载体中的沸石，该沸石可涂覆有氧化铝溶胶。
根据本发明的一个实施方案，重整前的沸石可为H-Beta沸石或CHA沸石。根据本发明的催化剂制品可进一步包含铂系组分以及NOx存储材料(例如，钡、锶和镁)，该铂系组分和NOx存储材料通常添加在NOx吸附型柴油氧化催化剂中。此外，在选择性催化还原催化剂或过滤型选择性催化还原催化剂中，可进一步包含本领域技术人员所理解的典型组分(诸如共轭物)。根据本发明的重整沸石可置于载体的内壁上或者载体内壁的孔中。
根据另一个实施方案，本发明可提供一种包含所述催化剂制品的废气处理***。
有益效果
根据本发明的重整沸石的稳定性可通过X射线衍射(XRD)和Brunauer EmmettTeller(BET)表面积变化来确认。在将涂覆有重整沸石的NA-DOC、SCR或SDPF催化剂施加到排气***时，高温废气的氮氧化物(NOx)的吸附率或转化率因沸石的耐热性改善而提高。此外，在暴露于高温废气时的热耐久性以及即使在暴露于高浓度硫和碱金属时依然保有的抗毒性也得到改善。
可能存在影响重整沸石稳定性的因素，诸如但不仅限于氧化铝的物理屏障作用(氧化铝充当沸石的壳，沸石为核心)以及脱铝作用的弱化。
附图说明
图1示出了新鲜重整沸石和老化重整沸石的透射式电子显微镜(TEM)分析的结果，图2b为示出了因老化所致变化的示意图；
图2示出了在按照使用共振声混合(RAM)型混合机和球磨工艺制备重整沸石的方法通过混合γ-氧化铝粉末而非氧化铝溶胶来制备重整沸石之后的TEM分析的结果；
图3a示出了在750℃至1200℃的温度下常规BEA沸石和重整BEA沸石的X射线衍射(XRD)谱，图3b示出了在750℃至1200℃的温度下常规SSZ13沸石和重整SSZ13沸石的XRD谱；
图4示出了在实验室管式炉(LTF)老化L/R工艺中，在800℃至950℃的温度下常规BEA沸石和重整BEA沸石的XRD谱；
图5示出了在LTF老化L/R工艺中，在800℃至950℃的温度下常规沸石和重整沸石的Brunauer Emmett Teller(BET)表面积变化的曲线图；
图6为示出了当在850℃的温度下执行持续25小时的湿热老化(HTA)、在100℃的温度下以400ppm的速率执行持续10分钟的NOx吸附以及在100℃至700℃的温度下执行解吸的条件下测量NOx吸附率时，各NA-DOC催化剂制品的NOx吸附率的曲线图，所述NA-DOC催化剂制品包含SSZ13沸石对照组(Pd/CHA)、γ-氧化铝(g-Al2O3)对照组和在对照组沸石中含有30wt％氧化铝溶胶的重整沸石(ZASA@NA-DOC)；
图7为示出了在催化剂制品经过25小时850℃下的HTA老化和12小时900℃下的HTA老化之后的氨气-SCR性能效率的曲线图，所述催化剂制品包含SSZ13沸石对照组(Ref-Cu/CHA)、γ-氧化铝(g-Al2O3)对照组和在对照组沸石中含有30wt％氧化铝溶胶的重整沸石(ZASA)；并且
图8为示出了在催化剂制品经过12小时900℃下的HTA老化之后的氨气-SCR性能效率的曲线图，在所述催化剂制品中，在DPF上涂覆有包含SSZ13沸石对照组(Ref-NOx)和在对照组沸石中含有30wt％氧化铝溶胶的重整沸石(ZASA)的催化剂。
具体实施方式
本发明涉及一种涂覆有氧化铝溶胶的重整沸石、在载体上置有该重整沸石的催化剂制品、以及包含该催化剂制品的废气处理***。
沸石是一种结晶硅酸铝材料，其通常具有直径为大约3至10埃的均匀孔径，该孔径取决于沸石的类型以及沸石晶格中所含的阳离子的类型和数量,它是具有孔尺寸的结晶铝硅酸盐水涂料。本领域的技术人员熟知沸石、合成沸石以及天然沸石用于促进特定反应的用途，包括以氨气充当还原剂对氮氧化物执行的选择性还原。本发明的目的是通过重整沸石，尤其是通过使用氧化铝溶胶制备重整沸石，来改善沸石的耐热性。本文所用的“氧化铝溶胶”一词可与“氢氧化铝”、“三羟铝石”或“勃姆石”互换使用。事实上，氧化铝溶胶被理解为一种包含若干形式的氢氧化铝的物质。一般来讲，氧化铝溶胶可视用途制备成粉末形式或饼块形式。在氧化铝溶胶的制备过程中，通过酸性水溶性铝盐(如氯化铝和硝酸铝)与碱性物质(如氢氧化铵和碳酸铵)的液相中和反应获得的水合氧化铝被执行老化和清洗以去除杂质，然后再进行过滤，于是便得到饼块形式的所需水合氧化铝，或者在干燥后通过热处理得到氧化铝溶胶粉末形式的所需水合氧化铝。
本发明中例示了H-Beta沸石、BEA沸石或CHA沸石并且例示了CHA沸石中的SSZ-13沸石，但并不仅限于这些材料。此外，沸石可与一个或多个金属阳离子发生离子交换，并且合适的金属包括但不仅限于铜、铁和钴。本发明中的沸石与氧化铝溶胶混合，所包含的氧化铝溶胶为沸石的大约5-50wt％，优选10-30wt％，它们的混合物将被干燥和煅烧以制备重整沸石。本发明的重整沸石具有卵-壳结构，沸石充当核心，氧化铝充当壳。
本发明的重整沸石被置于载体内壁的表面上或者载体内壁的孔中，从而形成NA-DOC、SCR或SDPF催化剂制品。本发明中的“催化剂制品”一词可与“催化剂”或“催化剂复合物”互换，并且“载体”一词可被描述为“基底”或“支撑物”。以蜂窝状基底作为载体的示例。本发明的催化剂制品可进一步包含常规添加剂。例如，NOx吸附型柴油氧化催化剂可进一步包含铂系组分、NOx存储材料(如钡、锶和镁)，选择性催化还原催化剂或过滤型选择性催化还原催化剂可进一步包含共轭物组分，该共轭物组分被置于耐火金属氧化物载体上以实现额外的催化功能。
本发明的催化剂制品安装在废气处理***上，并可进一步包含柴油氧化催化剂和/或位于催化剂制品上游的烟雾过滤器，并且催化剂制品的下游可设置有氨气氧化催化剂。
<沸石重整>
根据第一方法，提出了一种使用共振声混合(RAM)型混合机和球磨工艺的沸石重整方法。首先，将氧化铝溶胶溶液(30wt％)和BEA沸石(100wt％)混合到一起，然后向混合物中添加蒸馏水(DI)以制得具有30％固体含量的浆液。使用RAM混合机对浆液处理2分钟。送入氧化铝球，并通过湿磨法处理24小时，然后在150℃的温度下干燥，并在600℃的温度下煅烧，从而完成制备涂覆有重整沸石的氧化铝溶胶。在L/R条件下以700℃至1100℃的温度将新鲜沸石老化12小时。氧化铝溶胶溶液是指直径为2至10纳米的胶态分散体的溶液，通过将常见的5至50微米氧化铝粉末(诸如SASOL)注入到水或酸性溶液中来制得。
根据第二方法，提出了一种浆液过程。将氧化铝溶胶溶液(30wt％)和BEA沸石(100wt％)混合到一起，然后向混合物中添加蒸馏水(DI)，然后再对混合物执行持续10分钟的分散处理并调节酸度，从而制得具有30％固体含量的浆液。将产物在150℃的温度下干燥并在600℃的温度下煅烧，从而便制得了涂覆有重整沸石的氧化铝溶胶。在L/R条件下以700℃至1100℃的温度将新鲜沸石老化12小时。
所提出的用于制得重整沸石的第一方法和第二方法具有相同的特性。
图1a示出了新鲜重整沸石和老化重整沸石的透射式电子显微镜(TEM)分析的结果，图1b为示意图，示出了因老化所致的变化。新鲜重整沸石的尺寸为大约数百纳米，氧化铝组分集中在沸石周围。在实验室管式炉(LTF)中以850℃/12C将重整沸石老化(稀薄/高浓循环)，老化的沸石发生聚合并且尺寸减小至大约1μm。在这里，氧化铝组分实际上施加在沸石周围，从而使得形成卵-壳结构。具体地讲，在新鲜重整沸石中，集中在沸石周围的氧化铝在600℃的温度下煅烧，从而使得氧化铝呈γ-氧化铝形式，且新鲜重整沸石形成不致密的卵-壳。然而，在老化(即，在700至850℃温度下的烧结)之后，BET的结果显示，热稳定性变得优于未老化的新鲜沸石。
图2示出了在按照使用共振声混合(RAM)型混合机和球磨工艺制备重整沸石的方法通过混合γ-氧化铝粉末而非氧化铝溶胶来制备重整沸石之后的TEM分析的结果。沸石和氧化铝组分彼此分离，且不形成卵-壳结构。因此，用于为本发明中的沸石提供物理屏障的氧化铝前驱物必须仅限于氧化铝溶胶，并且优选地，在加入了老化过程时，沸石的特性得以进一步改善。
图3a示出了在750℃至1200℃的温度下常规BEA沸石和根据本发明的重整BEA沸石的XRD谱。常规BEA沸石在1200℃或更高的温度下显示新峰值，并在该温度下发生结构坍塌。然而，本发明的重整BEA沸石在高温下显示恒定的峰值，从而使得其结构具有结构稳定性。
图3b示出了在750℃至1200℃的温度下常规SSZ13沸石和根据本发明的重整SSZ13沸石的XRD谱。常规SSZ13沸石在1100℃或更高的温度下显示新峰值，并发生结构坍塌。然而，本发明的重整SSZ13沸石在1150℃或更高的温度下显示新峰值，这就意味着，重整SSZ13沸石保持结构稳定性的温度比未施加氧化铝溶胶的沸石要高50℃。
图4示出了在LTF老化L/R工艺中，在800℃至950℃的温度下常规BEA沸石和重整BEA沸石的XRD谱。当温度上升时，常规BEA沸石变得不稳定。然而，在900℃温度下持续12小时的L/R循环老化之后，本发明的重整BEA沸石更稳定。
图5示出了在LTF老化L/R工艺中，在800至950℃的温度下常规沸石和本发明的重整沸石的BET表面积变化的曲线图。由于表面积变化小于常规沸石，因此本发明的重整沸石显示出结构稳定性，而BEA沸石显示出比SSZ13沸石更稳定的曲线。
在本发明的另一个实施方案中，重整沸石可具有颗粒催化剂的形状，并通过将该颗粒形状置于载体上来提供催化剂制品。载体或基底可为通常用于制备催化剂的任意材料，并且通常包含陶瓷或金属蜂窝状结构。例如，陶瓷基底可由任意耐火材料形成。具体地讲，通过将重整沸石作为洗涂层施加到基底来制备根据本发明另一个实施方案的催化剂制品或催化剂复合物。重整沸石的洗涂层可使用粘接剂来制备。根据本发明的一个或多个实施方案，将合适的前驱物(诸如从氧锆基硝酸盐诱导的锆前驱物，例如ZrO2)用作粘接剂。根据另一个实施方案，重整沸石催化剂包含一种贵金属组分，即，铂系金属组分。例如，为了防止氨泄漏现象，通常在重整沸石催化剂中包含作为氨气氧化催化剂的铂系组分。合适的铂金属组分包括铂、钯、铑、以及它们的混合物。催化剂材料(例如，重整沸石和贵金属组分)的多种组分可作为耐火载体(即，两种或多种组分的洗涂层混合物)或者作为单独的洗涂层组分来施加。催化剂制品可使用已知方法形成。涂覆方法是熟知的，并且可以在载体的内壁表面上，或者在部分表面上，或者在内壁的其余部分上或者在壁的整个内部中执行承载。根据本发明的重整沸石催化剂制品可设置在废气处理***(诸如汽油车或柴油车中可见的***)中。在这些废气处理***中，重整沸石催化剂制品通常用于与催化剂制品上游或下游的其他气体处理制品实现流体连通，例如与柴油氧化催化剂、烟雾过滤器和/或氨气氧化催化剂制品实现流体连通。
图6为示出了当在850的℃温度下执行持续25小时的湿热老化(HTA)、在100℃的温度下以400ppm速率执行持续10分钟的NOx吸附以及在100℃至700℃的温度下执行解吸的条件下测量NOx吸附率时，各NA-DOC催化剂制品的NOx吸附率的曲线图，所述NA-DOC催化剂制品包含SSZ13沸石对照组(Pd/CHA)、γ-氧化铝(g-Al2O3)对照组和在对照组沸石中含有30wt％的氧化铝溶胶的重整沸石(ZASA@NA-DOC)。图6的NA-DOC包含CeO2-Al2O3，其含有铂系元素以及SSZ13沸石、γ-氧化铝和由氧化铝溶胶重整的沸石。参考图6，需注意的是，较之于含有SSZ13沸石对照组(Pd/CHA)的NA-DOC和含有γ-氧化铝(g-Al2O3)对照组的NA-DOC，含有本发明的重整沸石的NA-DOC的NOx吸收率改善了大约20％。
图7为为示出了在催化剂制品经过25小时850℃下的HTA老化和12小时900℃下的HTA老化之后的氨气-SCR性能效率的曲线图，所述催化剂制品包含SSZ13沸石对照组(Ref-Cu/CHA)、γ-氧化铝(g-Al2O3)对照组和在对照组中含有30wt％的氧化铝溶胶得改性沸石(ZASA)。在图7中，氨气-SCR反应的条件是：400ppm、NH3/NOx＝1且SV＝60,000hr-1，需注意的是，通过本发明制得的SCR催化剂制品的NOx转化率优于对照制品，且尤其是在高温下，转化率显著改善。
图8为示出了在催化剂制品经过12小时900℃下的HTA老化之后的氨气-SCR性能效率的曲线图，在所述催化剂制品中，在DPF上涂覆有包含SSZ13沸石对照组(Ref-NOx)和重整沸石(ZASA)的催化剂，该重整沸石在对照组沸石中含有30wt％的氧化铝溶胶。所使用的DPF是基于堇青石的过滤器，且涂覆量为250g/L。从图8可知，需注意的是，较之于对照组，响应于温度上升，ZASA的NOx转化率显著。
根据本发明的催化剂制品改善了高温下的催化剂效率。这种改善可归因于重整沸石的改善的耐热性。图9进一步支撑了这一结论。图9为示出了含有3％Cu的SSZ13沸石对照组、在对照组中含有10wt％氧化铝溶胶的重整沸石、以及在对照组中含有30wt％氧化铝溶胶的重整沸石在770℃/20贫燃、800℃/12C、850℃/12C条件下的BEA表面积变化的曲线图和表格：在的温度下以贫燃条件处理12小时、在的温度下处理12小时以及在850℃的温度下处理12小时。上述曲线图和表格显示，重整沸石具有改善的结构稳定性。

Claims (6)

1.一种氮氧化物吸附型柴油氧化催化剂制品，其包括置于载体上的沸石，其中所述沸石涂覆有氧化铝溶胶。
2.一种选择性催化还原催化剂制品，其包括置于载体上的沸石，其中所述沸石涂覆有氧化铝溶胶。
3.一种过滤型选择性催化还原催化剂制品，其包括置于载体上的沸石，其中所述沸石涂覆有氧化铝溶胶。
4.一种涂覆有氧化铝溶胶的沸石，其用在氮氧化物吸附型三效催化剂制品、选择性催化还原催化剂制品或过滤型选择性催化还原催化剂制品中。
5.根据权利要求1至3中任一项所述的催化剂制品，其中所述沸石为H-Beta沸石或CHA沸石。
6.一种废气处理***，其包括根据权利要求1至3中任一项所述的催化剂制品。
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