CN110605110A - 用于捕获氮氧化物和/或硫氧化物的纳米稀土氧化物掺杂的载体 - Google Patents

用于捕获氮氧化物和/或硫氧化物的纳米稀土氧化物掺杂的载体 Download PDF

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Publication number
CN110605110A
CN110605110A CN201910515336.4A CN201910515336A CN110605110A CN 110605110 A CN110605110 A CN 110605110A CN 201910515336 A CN201910515336 A CN 201910515336A CN 110605110 A CN110605110 A CN 110605110A
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catalyst support
catalyst
support
rare earth
exhibits
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D·谢泼德
C·齐斯科夫斯基
J·布朗
J·拉沙佩尔
W·吴
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Pacific Industrial Development Corp
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Pacific Industrial Development Corp
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Abstract

一种掺杂有纳米稀土氧化物颗粒的无机氧化物材料，其能够在低于400℃的温度下捕获NOx或SOx的一种或多种。纳米稀土氧化物颗粒的粒度小于10纳米。催化剂载体可以在低于350℃的温度下捕获至少0.5％的NO2和/或在低于325℃的温度下捕获至少0.4％的SO2。在800℃老化16小时后的催化剂载体可以在10％的蒸汽环境中在低于250℃的温度下捕获至少0.5％的NO2和/或至少0.2％的SO2。与常规稀土掺杂载体相比，在10％的蒸汽环境中，催化剂载体在低于400℃的温度下表现出对NOx或SOx的至少一种的捕获能力提高了至少25％。

Description

用于捕获氮氧化物和/或硫氧化物的纳米稀土氧化物掺杂的 载体
相关申请的交叉引用
根据35U.S.C§119(e)，本申请要求于2018年6月14日提交的美国临时申请第62/684932号的权益，其全部内容通过引用并入本文。
技术领域
本发明一般涉及用于催化应用的氧化物载体材料。更具体地说，这些氧化物载体材料显示出捕获废气流中存在的NOx和/或SOx排放物的能力。
背景技术
本节的陈述仅提供与本公开相关的背景信息，不构成现有技术。
各种氮氧化物如一氧化氮(NO)和二氧化氮(NO2)通常可以称为NOx，以及硫氧化物(SOx)、颗粒物(PM)和二氧化碳(CO2)，代表了烃燃料燃烧形成的空气污染类型。氮氧化物(NOx)通过在燃烧过程中产生的相对高温下的氮气和氧气反应形成。硫氧化物(SOx)排放物是由于烃燃料中作为杂质存在的各种硫化合物。由燃料燃烧引起的空气污染包括对人体健康有害的气体，以及对环境产生温室效应的气体。
选择性催化还原(SCR)和选择性非催化还原(SNCR)通过使废气与尿素或氨反应产生氮和水来还原后燃烧后的NOx。SCR现在被用于许多应用中，包括船舶、柴油卡车和一些汽车的废气处理中。在机动车辆发动机中使用废气再循环和催化转化器显著减少了车辆排放物。
此外，为了将NOx和SOx气体催化转化为其他化合物，当前的排放控制技术还利用各种主动和被动吸收剂来捕获或结合NOx和/或SOx。例如，NOx存储和还原(NSR)催化剂在由相应的空气与燃料比确定的贫环境(氧化)和富环境(还原)下循环运行。
全球排放法规趋向于减少允许的NOx排放物。当前和未来的法规正在将废气中可能存在的允许的NOx排放量减少90％或更多。在冷启动期间，来自车辆尾管的NOx排放物超过75％，这就导致在需要在不增加存在的催化剂的总量情况下相对于催化剂活性增加的NOx捕获能力。因此，需要由氧化物载体材料形成的催化剂或在氧化物载体材料上形成的催化剂，以满足这些新规定对增强的NOx或SOx捕获能力的要求。
发明内容
本公开一般涉及催化剂载体，其包含掺杂有纳米稀土氧化物颗粒的无机氧化物材料，使得催化剂载体能够在低于400℃的温度下捕获NOx或SOx中的一种或多种。纳米稀土氧化物颗粒可以是Ce的氧化物、Pr的氧化物、Nd的氧化物、La的氧化物、Y的氧化物、或其组合，而无机氧化物材料包括Al2O3、ZrO2、TiO2、SiO2、MgAl2O4、或其组合。纳米稀土氧化物颗粒的粒度可以小于10纳米(nm)。
根据本公开的另一方面，一种废气处理系统包括含金属的催化剂，其中所述含金属的催化剂包括上述催化剂载体材料以及本文进一步限定的一种或多种金属。所述一种或多种金属可以选自Cu、Fe、Co、Zr、Ti或其混合物。当需要时，其中壁流基材(wall flowsubstrate)的至少一部分可以用含金属的催化剂涂覆并适于与气流接触。
根据本公开的又一方面，催化剂载体可以用于形成三元催化剂、四元催化剂、柴油氧化催化剂或氧化催化剂，用于处理车辆废气。
根据本公开的又一方面，提供了一种在氧气存在下减少气流中所含的氮氧化物或硫氧化物的方法。该方法通常可以包括使气流与如上所述和本文进一步定义的含金属的催化剂接触。
根据本文提供的描述，其他适用领域将变得显而易见。应该理解的是，描述和具体实施例仅用于说明的目的，并不旨在限制本公开的范围。
附图说明
为了能够很好地理解本公开，现在将描述其各种形式，以实例的方式给出，参考附图，其中：
图1A是常规稀土掺杂的氧化铝载体的扫描电子显微照片；
图1B是图1A的常规载体的透射电子显微照片，显示了载体中铈和铝的位置；
图2A是图1A的常规稀土掺杂的氧化铝载体的更高放大倍数的扫描电子显微照片；
图2B是图2A的常规载体的透射电子显微照片，显示了载体中铈和铝的位置；
图3A是根据本公开的教导形成的纳米稀土掺杂的氧化铝载体的扫描电子显微照片；
图3B是图3A的纳米稀土载体的透射电子显微照片，显示了载体中铈和铝的位置；
图4A是图3A的纳米稀土掺杂的氧化铝载体的更高放大倍数的扫描电子显微照片；
图4B是图4A的纳米稀土载体的透射电子显微照片，显示了载体中铈和铝的位置；
图5A是在10％的蒸汽环境中，新鲜的常规稀土掺杂的载体和根据本公开制备的新鲜的纳米稀土掺杂的载体的NOx捕获的图形比较。
图5B是在800℃下老化16小时后的常规稀土掺杂的载体和根据本公开制备的纳米稀土掺杂的载体在10％的蒸汽环境中的NOx捕获的图形比较；以及
图6A是在10％的蒸汽环境中，新鲜的常规稀土掺杂的载体和根据本公开制备的新鲜的纳米稀土掺杂的载体的SOx捕获的图示；以及
图6B是在800℃下老化16小时后的常规稀土掺杂的载体和根据本公开制备的纳米稀土掺杂的载体在10％的蒸汽环境中的SOx捕获的图形比较。
这里描述的附图仅用于说明目的，并不旨在以任何方式限制本公开的范围。
具体实施方式
以下描述本质上仅是示例性的，并且决不旨在限制本公开或其应用或用途。例如，在本公开全文中描述了根据本文所包含的教导制备和使用的催化剂载体以及用于减少车辆排放气体的三元催化剂(TWC)，以便更充分地说明其组成及用途。在其他催化剂(例如四元催化剂、柴油氧化催化剂和氧化催化剂)中或在其他催化应用中引入和使用这种OSM预期在本公开的范围内。应该理解的是，在整个说明书中，相应的附图标记表示相似或相应的部件和特征。
由于在冷启动条件下超过75％的NOx和/或SOx排放物来自车辆的废气，因此催化剂和催化剂载体材料必须表现出提高的捕获NOx和/或SOx排放物的能力。本公开的催化剂载体解决该问题的方式是：在不增加所存在催化剂的量的情况下，使NOx和/或SOx排放物的低温至中温捕获相对于传统技术和常规载体材料提高超过50％。
本公开通常提供一种催化剂载体，其包含掺杂有纳米稀土氧化物颗粒的无机氧化物材料，或其由掺杂有纳米稀土氧化物颗粒的无机氧化物材料组成，或其基本上由掺杂有纳米稀土氧化物颗粒的无机氧化物材料组成。该催化剂载体能够在低于400℃的温度下捕获NOx或SOx中的一种或多种。
无机氧化物材料可以是本领域技术人员已知的能够用于催化应用的任何类型的氧化物载体材料。当需要时，无机氧化物材料可以是选自Al2O3、ZrO2、TiO2、SiO2、MgAl2O4或其组合的氧化物。或者，无机氧化物材料是Al2O3、SiO2、BaO或其组合。或者，无机氧化物材料是Al2O3、SiO2和ZrO2的组合。这些组合可以是简单地将不同的氧化物材料混合在一起或将不同的氧化物整合到共用的骨架结构中而得到，所述骨架结构例如是由硅铝酸盐如沸石等形成的骨架结构。
当需要时，相对于催化剂载体的总重量，催化剂载体可以具有的无机氧化物的含量范围为约20重量％至99.9重量％、或约30重量％至约99重量％、或约40重量％至约90重量％、或约50重量％至约80重量％。催化剂载体中的纳米稀土氧化物的含量范围也可以为0.1重量％至约80重量％、或约1重量％至约70重量％、或约10重量％至约60重量％、或约20重量％至约50重量％。
根据本公开的另一方面，存在于催化剂载体中的纳米稀土氧化物颗粒可以选择为包括，但不限于，铈(Ce)的氧化物、镧(La)的氧化物、钕(Nd)的氧化物、镨(Pr)的氧化物、钇(Y)的氧化物、或其组合。这些纳米稀土氧化物颗粒的平均粒度(D50)为小于约10纳米(nm)、或者小于约8纳米、或者约1纳米至约10纳米。测得纳米稀土氧化物的最大粒度为约50纳米、或小于40纳米、或小于25纳米、或小于10纳米。
催化剂载体表现出的表面积范围可以为约25m2/g至约500m2/g，并且孔体积(PV)的范围为0.05cc/g至约2.0cc/g。或者，催化剂载体表现出的表面积范围可以为约50m2/g至约350m2/g、或约100m2/g至约200m2/g。或者，催化剂载体表现出的孔体积(PV)的范围可以为0.1cc/g至约1.5cc/g、或约0.3cc/g至约1.0cc/g。
在老化(催化剂载体在800℃保持约16小时)后，在10％的蒸汽环境中，催化剂载体表现出的表面积和孔体积可以比新制备催化剂载体时测量的值低。然而，在这种老化后，催化剂载体表现出的表面积仍然为至少25m2/g、或者50m2/g或更大，并且孔体积为至少0.1cc/g、或者0.2cc/g或更高。
现在参考图1A和图2A，扫描电子显微镜(SEM)可以用于提供常规稀土氧化物载体(C-1)的图像，放大倍数分别高达1微米(μm)或高达300纳米(nm)。该常规载体(C-1)表示涂覆在氧化铝(Al)材料上的二氧化铈(Ce)的组合或浸渍于氧化铝(Al)材料中的二氧化铈(Ce)的组合。常规稀土氧化物载体可以通过本领域技术人员已知的任何方法制备。
透射电子显微镜(TEM)可以与SEM结合使用，以分析常规稀土氧化物载体(C-1)的表面，如图1B和2B所示。这些常规载体的表面通常含有大量的氧化铝(Al)，以及其上分散有二氧化铈(Ce)的离散袋(pocket)或区域。
通过用硝酸铈溶液浸渍表面积为200m2/g和孔体积为1.0cc/g的γ氧化铝来制备常规稀土氧化物载体(C-1)。更具体地说，将70克γ氧化铝放入混合器中，并将100克含有含量为30％的CeO2的硝酸铈溶液喷到载体上。将载体混合并在120℃下干燥12小时，然后在600℃下煅烧4小时。得到的常规载体(C-1)是含有30％二氧化铈的二氧化铈掺杂的γ氧化铝载体。
现在参考图3A和图4A，扫描电子显微镜(SEM)用于提供根据本公开的教导制备的纳米稀土氧化物载体(R-1)的显微照片，放大倍数分别高达1微米(μm)或高达300纳米(nm)。该催化剂载体(R-1)表示涂覆在氧化铝(Al)材料上的二氧化铈(Ce)纳米颗粒的组合或浸渍于氧化铝(Al)材料中的二氧化铈(Ce)纳米颗粒的组合。根据本公开的教导制备的稀土氧化物载体可以使用本领域技术人员已知的任何方法完成，包括但不限于共沉淀和/或浸渍。
透射电子显微镜(TEM)可以与SEM结合使用以分析催化剂载体(R-1)的表面，如图3B和4B所示。这些催化剂载体的表面通常含有大量分散在氧化铝(Al)材料上或浸渍在氧化铝(Al)材料中的二氧化铈(Ce)纳米颗粒。
通过用胶态二氧化铈溶液浸渍表面积为200m2/g和孔体积为1.0cc/g的γ氧化铝来制备催化剂载体(R-1)。更具体地说，将70克γ氧化铝放入混合器中，并将100克含有含量为30％的CeO2的胶态二氧化铈溶液喷到载体上。将载体混合并在120℃干燥12小时，然后在600℃煅烧4小时。得到的催化剂载体(R-1)是含有30％二氧化铈的二氧化铈掺杂的γ氧化铝载体。
现在参考图5A和图6A，将本公开的催化剂载体(R-1)捕获的NOx和/或SOx的量与常规稀土掺杂的氧化物载体(C-1)捕获的量进行比较。如图5A所示，催化剂载体(R-1)可以在蒸汽环境中，在低于约350℃、或约150℃至约350℃、或约200℃至300℃的温度下捕获至少0.5％的NO2。如图6A所示，催化剂载体(R-1)可以在蒸汽环境中，在低于约325℃、或约150℃至约325℃的温度下捕获至少0.4％的SO2。
仍然参考图5A和图6A，在相同的温度范围内，可以被本公开的催化剂载体(R-1)捕获的NOx和/或SOx的量大于常规稀土掺杂的载体(C-1)捕获的量。实际上，在10％的蒸汽环境中，与常规稀土掺杂的载体(C-1)相比，催化剂载体(R-1)在低于400℃的温度下捕获NOx或SOx中的至少一种的能力提高至少25％。或者，在10％的蒸汽环境中，与常规稀土掺杂的载体(C-1)相比，催化剂载体(R-1)在低于350℃的温度下捕获NOx或SOx中的至少一种的能力提高至少40％。或者，在10％的蒸汽环境中，与常规稀土掺杂的载体(C-1)相比，催化剂载体(R-1)在低于325℃的温度下捕获NOx或SOx中的至少一种的能力提高至少50％。
现在参考图5B和图6B，根据本公开制备的催化剂载体在使用预定时间后可能会经历NOx和/或SOx捕获性能的降低。但是，如图5B所示，在800℃老化16小时后的催化剂载体(R-1)在10％的蒸汽环境中在低于250℃的温度下仍能够捕获至少0.5％的NO2。此外，如图6B所示，在800℃老化16小时后的催化剂载体(R-1)在10％的蒸汽环境中在低于250℃的温度下仍能够捕获至少0.2％的SO2。
仍然参考图5B和图6B，与老化的常规载体(C-1)相比，老化的催化剂载体(R-1)仍然表现出提高量的对NOx和/或SOx的捕获能力。实际上，在800℃下老化16小时后，与常规稀土掺杂的载体(C-1)相比，在10％的蒸汽环境中，催化剂载体(R-1)在低于400℃的温度下表现出对NOx或SOx中的至少一种的捕获能力提高了至少10％。或者，在800℃下老化16小时后，与常规稀土掺杂的载体(C-1)相比，在10％的蒸汽环境中，催化剂载体(R-1)在低于350℃的温度下表现出对NOx或SOx中的至少一种的捕获能力提高了至少20％。或者，在800℃下老化16小时后，与常规稀土掺杂的载体(C-1)相比，在10％的蒸汽环境中，催化剂载体(R-1)在低于300℃的温度下表现出对NOx或SOx中的至少一种的捕获能力提高了至少30％。
出于本公开的目的，术语“捕获的”或“捕获”是指在催化剂载体的表面处吸附NOx和/或SOx，或通过催化剂载体本体吸收NOx和/或SOx，或两者均发生。本领域技术人员将理解，在催化剂载体捕获NOx和/或SOx之后，可以通过使用一种或多种机制解吸NOx和/或SOx来再生催化剂载体，所述机制包括但不限于与富含烃的气氛以反应产生水和氮。
根据本发明的另一方面，催化剂载体可以用于形成三元催化剂、四元催化剂、柴油氧化催化剂或氧化催化剂，从而用于处理车辆废气。当以这种方式使用催化剂载体时，提供了废气处理系统。该废气处理系统通常包括含金属的催化剂，该催化剂包含由本文定义的催化剂载体以及一种或多种金属，或由本文定义的催化剂载体以及一种或多种金属组成，或基本上由本文定义的催化剂载体以及一种或多种金属组成。存在于含金属的催化剂中的金属可以是铂族金属。当需要时，金属可以选自，但不限于，铜(Cu)、铁(Fe)、镍(Ni)、钴(Co)、锰(Mn)、锆(Zr)、或钛(Ti)、或其组合。或者，金属包括Cu、Fe、Co、Zr或Ti中的一种或多种。存在于含金属的催化剂中的金属的量的范围可以为0重量％至8重量％、或者约1重量％至约7重量％、或者约2重量％至约5重量％，其余为催化剂载体。
可以形成废气处理系统，其中壁流基材的至少一部分、过滤器或整个系统涂覆有含金属的催化剂并适于与气流接触。在这种情况下，含金属的催化剂可以不受限制地施加作为洗涤涂层。当需要时，壁流基材可以包括蜂窝结构。
根据本公开的又一方面，提供了一种在氧气存在下减少气流中所含的氮氧化物或硫氧化物的方法。该方法通常包括使气流与如上所述以及如本文进一步定义的含金属的催化剂接触。
出于本公开的目的，由于本领域技术人员已知的预期变化(例如，测量上的限制和可变性)，本文对于可测量值和范围使用了术语“约”和“基本上”。
出于本公开的目的，术语“重量”是指质量值，例如单位克、千克等。此外，通过端点列举的数值范围包括端点和该数值范围内的所有数字。例如，40重量％至60重量％的浓度范围包括浓度为40重量％、60重量％，以及其间的所有浓度(例如，40.1％、41％、45％、50％、52.5％、55％、59％等)。
出于本公开的目的，术语要素的“至少一个”和“一个或多个”可以互换使用，并且可以具有相同的含义。这些术语指的是包括单个要素或多个要素。例如，“至少一种金属”，“一种或多种金属”和“金属”可以互换使用，并且旨在具有相同的含义。
在本说明书中，已经以能够写出清楚和简明的说明书的方式描述了实施方案，但是其目的在于并且将理解，可以在不脱离本发明的情况下以各种方式组合或分割实施方案。例如，应当理解，本文描述的所有优选特征适用于本文描述的本发明的所有方面。
根据本公开内容，本领域技术人员将理解，在不脱离或超出本公开的精神或范围的情况下，可以在本文公开的具体实施方案中进行许多改变，并且仍然获得相同或相似的结果。本领域技术人员将进一步理解，本文公布的任何性质代表常规测量的性质，并且可以通过多种不同方法获得。本文描述的方法代表一种这样的方法，并且可以在不超出本公开的范围的情况下使用其他方法。
已经出于说明和描述的目的呈现了本发明的多种形式的前述描述。其并非旨在穷举或将本发明限制于所公开的精确形式。鉴于上述教导，可以进行许多改变或变化。选择和描述所讨论的形式以提供本发明原理及其实际应用的最佳说明，从而使得本领域普通技术人员能够以多种形式和适合于预期的特定用途的多种改变来使用本发明。当根据它们公平、合法和公正地授权范围进行解释时，所有这些改变和变化都在由所附权利要求确定的本发明的范围内。

Claims (20)

1.一种催化剂载体，包含掺杂有纳米稀土氧化物颗粒的无机氧化物材料，使得所述催化剂载体能够在低于400℃的温度下捕获氮氧化物或硫氧化物中的一种或多种。
2.根据权利要求1所述的催化剂载体，其中所述纳米稀土氧化物颗粒是Ce的氧化物、Pr的氧化物、Nd的氧化物、La的氧化物、Y的氧化物或其组合。
3.根据权利要求1或2中任一项所述的催化剂载体，其中所述纳米稀土氧化物颗粒的粒度小于10纳米。
4.根据权利要求1或2中任一项所述的催化剂载体，其中所述无机氧化物材料是Al2O3、ZrO2、TiO2、SiO2、MgAl2O4或其组合。
5.根据权利要求1或2中任一项所述的催化剂载体，其中所述纳米稀土氧化物颗粒存在的量的范围为所述催化剂载体总重量的0.1重量％至约80重量％，并且所述无机氧化物材料存在的量的范围为所述催化剂载体总重量的约20重量％至约99.9重量％。
6.根据权利要求1或2中任一项所述的催化剂载体，其中所述催化剂载体表现出的表面积范围为约50m2/g至约350m2/g。
7.根据权利要求6所述的催化剂载体，其中所述催化剂载体表现出的表面积范围为约100m2/g至约200m2/g。
8.根据权利要求1或2中任一项所述的催化剂载体，其中所述催化剂载体表现出的孔体积范围为0.1cc/g至约1.5cc/g。
9.根据权利要求8所述的催化剂载体，其中所述催化剂载体表现出的孔体积范围为约0.3cc/g至约1.0cc/g。
10.根据权利要求1或2中任一项所述的催化剂载体，其中在800℃老化16小时后的所述催化剂载体在10％的蒸汽环境中表现出大于50m2/g的表面积。
11.根据权利要求1或2中任一项所述的催化剂载体，其中在800℃老化16小时后的所述催化剂载体在10％的蒸汽环境中表现出大于0.2cc/g的孔体积。
12.根据权利要求1或2中任一项所述的催化剂载体，其中在10％的蒸汽环境中，所述催化剂载体在约200℃至约350℃的温度下捕获至少0.5％的NO2和/或在约150℃至约325℃的温度下捕获至少0.4％的SO2。
13.根据权利要求1或2中任一项所述的催化剂载体，其中在800℃老化16小时后的所述催化剂载体在10％的蒸汽环境中在低于250℃的温度下捕获至少0.5％的NO2和/或至少0.2％的SO2。
14.根据权利要求1或2中任一项所述的催化剂载体，其中，与常规稀土掺杂的载体相比，在10％的蒸汽环境中，在低于400℃的温度下，所述催化剂载体表现出对氮氧化物或硫氧化物的至少一种的捕获能力提高至少25％。
15.根据权利要求1或2中任一项所述的催化剂载体，其中，在800℃下老化16小时后，与常规稀土掺杂的载体相比，在10％的蒸汽环境中，在低于350℃的温度下，所述催化剂载体对氮氧化物或硫氧化物的至少一种的捕获能力提高至少20％。
16.根据权利要求1或2中任一项所述的催化剂载体在用于处理车辆废气的三元催化剂、四元催化剂、柴油氧化催化剂或氧化催化剂中的用途。
17.一种废气处理系统，包括含金属的催化剂，其中所述含金属的催化剂包含根据权利要求1所述的催化剂载体材料和一种或多种金属。
18.根据权利要求17所述的废气处理系统，其中所述金属选自Cu、Fe、Co、Zr、Ti或其混合物。
19.根据权利要求17或18中任一项所述的废气处理系统，其中壁流基材的至少一部分涂覆有所述含金属的催化剂并适于与气流接触。
20.一种在氧气存在下减少气流中所含的氮氧化物或硫氧化物的方法，其中所述方法包括使所述气流与权利要求17或18中任一项所涉及的含金属的催化剂接触。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070014710A1 (en) * 2003-09-03 2007-01-18 Olga Gerlach Catalyst for removing pollutants from exhaust gases from lean-burn engines, with ruthenium as active metal
CN101687177A (zh) * 2007-06-27 2010-03-31 丰田自动车株式会社 催化剂载体和排气净化催化剂
US20100111789A1 (en) * 2006-08-31 2010-05-06 Franck Fajardie Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate
CN102489294A (zh) * 2011-12-22 2012-06-13 国电科学技术研究院 一种挤出成型的低温scr催化剂及其制备方法
US20150038325A1 (en) * 2012-03-14 2015-02-05 N.E. Chemcat Corporation Catalyst composition for exhaust gas cleaning and catalyst for automobile exhaust gas cleaning
CN105126808A (zh) * 2015-07-03 2015-12-09 河海大学 一种氧化铝担载型二氧化铈粉体材料的制备方法
US20160059225A1 (en) * 2014-08-29 2016-03-03 Dan Xie Small crystal ltl framework type zeolites

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4863596B2 (ja) 2001-06-18 2012-01-25 日産自動車株式会社 排気ガス浄化システム
US7723257B2 (en) * 2001-10-10 2010-05-25 Dominique Bosteels Process for the catalytic control of radial reaction
US7229600B2 (en) * 2003-01-31 2007-06-12 Nanoproducts Corporation Nanoparticles of rare earth oxides
GB0428557D0 (en) * 2004-12-30 2005-02-09 Magnesium Elektron Ltd Thermally stable doped and undoped porous aluminium oxides and nanocomposite CeO -ZrO and A1 O containing mixed oxides
US7357903B2 (en) * 2005-04-12 2008-04-15 Headwaters Heavy Oil, Llc Method for reducing NOx during combustion of coal in a burner
US8580701B2 (en) * 2010-11-19 2013-11-12 Corning Incorporated Method of controlling Ce:Zr ratio in oxide nanoparticles
RU2698675C2 (ru) * 2013-12-23 2019-08-28 Родиа Операсьон Неорганический оксидный материал

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070014710A1 (en) * 2003-09-03 2007-01-18 Olga Gerlach Catalyst for removing pollutants from exhaust gases from lean-burn engines, with ruthenium as active metal
US20100111789A1 (en) * 2006-08-31 2010-05-06 Franck Fajardie Catalyst/catalyst support compositions having high reducibility and comprising a nanometric cerium oxide deposited onto a support substrate
CN101687177A (zh) * 2007-06-27 2010-03-31 丰田自动车株式会社 催化剂载体和排气净化催化剂
CN102489294A (zh) * 2011-12-22 2012-06-13 国电科学技术研究院 一种挤出成型的低温scr催化剂及其制备方法
US20150038325A1 (en) * 2012-03-14 2015-02-05 N.E. Chemcat Corporation Catalyst composition for exhaust gas cleaning and catalyst for automobile exhaust gas cleaning
US20160059225A1 (en) * 2014-08-29 2016-03-03 Dan Xie Small crystal ltl framework type zeolites
CN105126808A (zh) * 2015-07-03 2015-12-09 河海大学 一种氧化铝担载型二氧化铈粉体材料的制备方法

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