CN106163659B - 在低温下通过固态离子交换来生产金属交换的沸石的方法 - Google Patents

在低温下通过固态离子交换来生产金属交换的沸石的方法 Download PDF

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CN106163659B
CN106163659B CN201480077685.8A CN201480077685A CN106163659B CN 106163659 B CN106163659 B CN 106163659B CN 201480077685 A CN201480077685 A CN 201480077685A CN 106163659 B CN106163659 B CN 106163659B
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zeolite
mixture
metal exchange
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CN106163659A (zh
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T·V·W·詹森斯
P·N·R·文内斯特罗姆
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Abstract

本发明公开了用于制备金属交换的沸石或金属交换的沸石的混合物(如Cu‑SSZ‑13、Cu‑ZSM‑5、Cu‑β或Fe‑β)的方法，该方法包括以下步骤：提供含有以下物质的干混合物：a)一种或多种显示离子交换能力的微孔沸石型材料，和b)一种或多种金属化合物；将混合物在含有氨的气氛中加热至低于300℃的温度并持续一定时间，其足以引发和进行金属化合物的离子和沸石材料的离子的固态离子交换；以及获得金属交换的沸石材料。

Description

在低温下通过固态离子交换来生产金属交换的沸石的方法
本发明涉及一种通过在低于300℃的温度下使金属氧化物或金属盐或其组合与具有离子交换能力的沸石材料的物理混合物暴露于含有氨的气氛来制备金属交换的沸石材料的方法。
沸石的离子交换能力源自这样的事实：结晶微孔骨架中的某些具有4+的形式价态的硅原子被具有3+的形式电荷的铝原子同晶置换。这在沸石晶体中产生了负电荷，其被阳离子如H+、NH4+、Na+或K+所平衡。铜和铁阳离子也可以形成合适的阳离子以平衡该负电荷，这是Cu和Fe交换的沸石可以通过上述方法生产的原因。
用Fe或Cu交换的沸石材料是用于例如电厂的废气中或固定或运输应用二者中的柴油发动机的废气中的NOx的催化还原的有效催化剂。例如，铜-β沸石、铁-β沸石、Cu-SSZ-13、Cu-ZSM-5是已知的用于从废气中去除NOx的催化剂。
NOx的催化还原被称为SCR(选择性催化还原)。两种最有名的还原NOx的SCR工艺类型是：(1)烃SCR(HC-SCR)，其中烃被用作还原剂，和(2)氨-SCR(NH3-SCR)，其中氨被用作还原剂。在用于去除柴油发动机废气中的NOx的烃-SCR的情况下，烃源是发动机的柴油燃料或者废气中由于发动机中的不完全燃烧而残留的烃。使用NH3-SCR的通用技术是在废气流中注入尿素，其分解以产生所需的用于SCR反应的NH3。
产生金属交换的沸石的一般方法是使沸石与期望的金属离子的溶液接触，随后过滤、洗涤、干燥和煅烧。因此，按照该一般程序，使沸石与含有Cu或Fe离子的适当溶液如硝酸铜、乙酸铜、硝酸铁、硫酸铜或硫酸铁接触通常会产生这样的材料：其在用烃或NH3进行的SCR反应中显示催化活性，该沸石为H+、NH4 +形式或者用不同阳离子进行离子交换。金属盐的阴离子的选择在原则上是任意的，但通常选择阴离子，使得获得足够的溶解度，能够在生产期间容易地去除，可安全地操作，并且不以不利的方式与沸石发生相互作用。
由于用于在沸石中引入金属离子的常规方法意味着操作适当的金属盐的一种或多种水溶液，所以基于这样的方法生产离子交换的沸石会包括过滤、干燥，以及最后的煅烧。
在沸石材料中引入离子的可备选方法是固态离子交换，其包括制备沸石材料和待引入至微孔晶体中的阳离子源的干混合物，以及随后的会驱动阳离子进入微孔材料中的一些适当处理。(G.L.Price,in:,J.R.Regalbuto(Ed.),Catalyst Preparation:Science andEngineering,CRC Press,Boca Raton,London,New York,2007,pp.283–296.)
专利EP955080公开了用于将Cu、Fe、Co、Mn、Pd、Rh或Pt通过以下方法引入至具有大于5的Si/Al比的沸石中的方法：在室温和大气压下物理混合(i)铵盐、NH3/NH4 +-沸石或含N化合物，和(ii)具有大于5的Si/Al比的沸石，以及(iii)选自上述金属的一种或多种化合物的活性化合物，并加热到至少300℃，直到离子交换过程完成；随后冷却至室温。在加热过程中，优选将该混合物暴露于氨或含胺的气氛，并且加热速率大于10K/分钟。
我们已经观察到：当通过使金属氧化物和/或盐与沸石材料的物理混合物暴露于含有气态NH3的气氛中来进行时，可以通过在250℃(其远低于EP955080中公开的下限)下进行固态离子交换来实现金属交换的沸石材料的制备。
本发明的优点是，可以在较低温度下制备SCR活性的沸石材料，因此降低了在引入金属离子的过程中损坏这些材料的风险，并且使得生产过程是更加成本有效的。
根据上述观察，本发明提供了用于制备金属交换的沸石材料或金属交换的沸石材料的混合物的固态离子交换方法，该方法包括以下步骤：提供含有以下物质的干混合物：a)一种或多种显示离子交换能力的沸石起始材料，和b)一种或多种金属化合物；将混合物在含有氨的气氛中加热到高至300℃的温度并持续一定时间，其足以引发和进行金属化合物的离子和一种或多种沸石的离子的固态离子交换；以及获得结晶的金属交换的沸石材料或金属交换的沸石材料的混合物。
可以在根据本发明的方法中使用的沸石材料可以是任何具有离子交换能力的沸石材料。优选地，沸石材料具有被命名为以下的晶体结构：AEI、AFX、CHA、KFI、LTA、IMF、ITH、MEL、MFI、SZR、TUN、*BEA、BEC、FAU、FER、MOR、LEV。
在一个实施方案中，一种或多种沸石起始材料选自由ZSM-5、沸石Y、β-沸石、SSZ-13、SSZ-39、SSZ-62和菱沸石组成的组。
在再一个实施方案中，一种或多种沸石起始材料是H+或NH4 +形式。
还在另一个实施方案中，一种或多种沸石起始材料含有有机结构导向剂。
在再一个实施方案中，一种或多种金属化合物选自选自由金属氧化物、金属硝酸盐、金属磷酸盐、金属硫酸盐、金属草酸盐、金属乙酸盐或其组合组成的组。
在一个实施方案中，一种或多种金属化合物中的金属选自由Fe、Co、Cu或其组合组成的组。
在一个实施方案中，金属化合物为CuO或Cu2O或其混合物。
在一个实施方案中，氨在气氛中的含量为1至5000体积ppm。
还在一个实施方案中，氧在气氛中的含量为10体积％或更少。
还在一个实施方案中，水在气氛中的含量为5体积％或更少。
在再一个实施方案中，在100至300℃，优选150至250℃的温度下使一种或多种显示离子交换能力的沸石起始材料与一种或多种金属化合物的混合物暴露于含有氨的气氛中。
实施例1
该实施例表明，通过本发明的方法获得了用于SCR的活性催化剂。通过将CuO与H-ZSM-5沸石混合至12.5wt％的CuO含量来制备催化剂。将催化剂的样品置于石英U形管反应器中，并在氮气中含有500ppm的NH3的气氛中在250℃下加热10小时。加热后，将催化剂冷却至200℃并暴露于在N2中的500ppm的NO、533ppm的NH3、5％的H2O和10％的O2的气体混合物，并在2700标升/克催化剂小时的空间速度下测定NO的转化率，作为用于材料的SCR活性的记录。
在250℃下在NH3中处理CuO与H-ZSM-5的混合物之后，所测量的NO的转化率为36.0％。为了比较，在未处理的CuO与H-ZSM-5的混合物上在相同条件下测量的NOx的转化率为1.4％，其表明气态NH3的存在对于在300℃下生产用于SCR的活性催化剂而言是至关重要的。
实施例2
该实施例表明，在暴露于氨时，避免氧气和水的存在是有利的。如实施例1所述制备催化剂样品。将催化剂的样品置于石英U形管反应器中，并在含有500ppm的NH3，还含有10％氧气或同时含有10％氧气和5％水的气氛中在250℃下加热10小时。加热后，将催化剂冷却至200℃并暴露于在N2中的500ppm的NO、533ppm的NH3、5％的H2O和10％的O2的气体混合物，并在2700标升/克催化剂小时的空间速度下测定NO的转化率，作为用于材料的SCR活性的记录。
在CuO与H-ZSM-5的混合物是在含有NH3和O2的气氛中处理的情况下，转化率为10.6％；在同时含有O2和H2O的气氛中处理的情况下，转化率为2.0％。
实施例3
该实施例表明，可以通过根据本发明的方法使用Cu2O在低于300℃下制备用于SCR的活性催化剂。通过在研钵中研磨来制备10wt％的Cu2O与H-ZSM-5沸石的干混合物。将该混合物的样品置于石英U形管反应器中，并在氮气中加热到100至250℃的预定温度。在达到期望的温度后，将500ppm的NH3加入到气流中5小时。在该处理之后，通过在氮气中冷却至160℃，并且使粉末混合物暴露于由在N2中的500ppm的NO、533ppm的NH3、5％的H2O和10％的O2组成的气氛来测定所得材料的催化活性，并在2700标升/克催化剂小时的空间速度下测定NOx的转化率，作为用于材料的SCR活性的记录。然后，使反应温度升高到180至200℃并在相同条件下测定各温度下的NOx转化率。
表1中给出了分别在100、150、200和250℃下在500ppm的NH3中制备的金属交换的沸石在SCR反应中的NOx转化率。
表1.在各种不同温度下在NH3中处理5小时后对Cu2O+H-ZSM-5混合物所得的NOx转化率

Claims (14)

1.用于制备金属交换的沸石材料或金属交换的沸石材料的混合物的方法，所述方法包括以下步骤：提供含有以下物质的干混合物：a)一种或多种显示离子交换能力的沸石起始材料，和b)一种或多种金属化合物，其中所述金属化合物为Cu(I)氧化物；将混合物在含有氨的气氛中加热到高至300℃的温度并持续一定时间，其足以引发和进行金属化合物的离子和一种或多种沸石的离子的固态离子交换；以及获得金属交换的沸石材料或金属交换的沸石材料的混合物。
2.根据权利要求1所述的方法，其中所述一种或多种沸石起始材料具有AEI、AFX、CHA、KFI、LTA、IMF、ITH、MEL、MFI、SZR、TUN、*BEA、BEC、FAU、FER、MOR、LEV的框架代码。
3.根据权利要求1或2所述的方法，其中所述一种或多种沸石起始材料选自由ZSM-5、沸石Y、β-沸石、SSZ-13、SSZ-39、SSZ-62和菱沸石组成的组。
4.根据权利要求1或2所述的方法，其中所述一种或多种沸石起始材料是H+或NH4 +形式。
5.根据权利要求1或2所述的方法，其中所述一种或多种沸石起始材料含有有机结构导向剂。
6.根据权利要求1或2所述的方法，其中氨在所述气氛中的含量为1至5000体积ppm。
7.根据权利要求1或2所述的方法，其中氧在所述气氛中的含量为10％或更少。
8.根据权利要求1或2所述的方法，其中水在在所述气氛中的含量为5体积％或更少。
9.根据权利要求1或2所述的方法，其中将所述一种或多种显示离子交换能力的沸石起始材料与一种或多种金属化合物的混合物在含有氨的气氛中加热到100至300℃的温度。
10.根据权利要求1或2所述的方法，其中将所述一种或多种显示离子交换能力的沸石起始材料与一种或多种金属化合物的混合物在含有氨的气氛中加热到150至250℃的温度。
11.一种金属交换的沸石或金属交换的沸石的混合物，其是通过根据权利要求1至10中任一项所述的方法获得的。
12.一种通过用还原剂进行选择性催化还原而从废气中除去氮氧化物的方法，所述方法包括使所述废气与包含通过根据权利要求1至10中任一项所述的方法获得的金属交换的沸石或金属交换的沸石的混合物的催化剂接触。
13.根据权利要求12所述的方法，其中所述还原剂是氨或其前体。
14.根据权利要求12所述的方法，其中所述还原剂包括烃。
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