CN106132541B - 在低温下通过固态离子交换来生产金属交换的金属铝磷酸盐的方法 - Google Patents

在低温下通过固态离子交换来生产金属交换的金属铝磷酸盐的方法 Download PDF

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CN106132541B
CN106132541B CN201480077684.3A CN201480077684A CN106132541B CN 106132541 B CN106132541 B CN 106132541B CN 201480077684 A CN201480077684 A CN 201480077684A CN 106132541 B CN106132541 B CN 106132541B
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exchange
metalloaluminophosphate
mixture
micropore
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CN106132541A (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结晶微孔金属铝磷酸盐或含有金属交换的微孔金属铝磷酸盐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金属铝磷酸盐起始材料，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至一定温度和持续一定时间，其足以引发和进行金属化合物的离子和结晶微孔材料的离子的固态离子交换；以及获得金属交换的微孔金属铝磷酸盐材料或含有金属交换的微孔金属铝磷酸盐材料的混合物。

Description

在低温下通过固态离子交换来生产金属交换的金属铝磷酸盐 的方法
本发明涉及一种通过使金属氧化物或金属盐或其组合与具有离子交换能力的结晶微孔金属铝磷酸盐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结晶微孔金属铝磷酸盐材料的方法。
金属铝磷酸盐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5+或3+的形式价态的磷原子或铝原子分别被具有不同的形式电荷的原子同晶置换。这在金属铝磷酸盐中产生了负电荷，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交换的金属铝磷酸盐可以通过上述方法生产的原因。
术语金属铝磷酸盐是指这样的铝磷酸盐材料：其中结晶骨架中的某些磷或铝或其组合被选自由金属、硅和锗组成的组中的一种或多种原子同晶置换。这样的材料的已知例子是硅铝磷酸盐(SAPO)、钛铝磷酸盐、锡铝磷酸盐。
用Cu或Fe交换的金属铝磷酸盐材料是用于例如电厂的废气中或固定和运输应用两者中的柴油发动机的废气中的NOx还原的有效催化剂。这样的材料的已知最好的例子是用Cu交换的SAPO-34。
NOx的催化还原被称作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。在烃-SCR的情况下，烃源是柴油(也用于柴油机)或废气中由于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。Cu-SAPO-34是用于两种类型的SCR反应的已知催化剂。
产生金属交换的结晶微孔金属铝磷酸盐的一般方法是使结晶微孔金属铝磷酸盐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，按照该一般方法，使结晶微孔金属铝磷酸盐与含有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，该微孔金属铝磷酸盐为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。
在结晶微孔金属铝磷酸盐中引入金属离子的常规方法往往是不太有效的。已知的是，为了用SAPO-34材料在选择性催化还原中获得足够高的活性，需要在高温下(>750℃)进行活化(P.N.R.A.Katerinopoulou,R.R.Tiruvalam,A.Kustov,P.G.Moses,P.Concepcion,A.Corma,ACS Catal.2013,3,2158–2161)。已经表明，这样的加热方法导致Cu在整个SAPO-34晶体中的重新分布，意味着初始的水相交换并非是不重要的。
在结晶微孔金属铝磷酸盐材料引入离子的可备选方法是固态离子交换，其包括制备结晶微孔金属铝磷酸盐材料和待引入至微孔晶体中的阳离子源的物理混合物，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 and Engineering,CRC Press,Boca Raton,London,NewYork,2007,pp.283–296.)。
专利申请US 2013/0108544公开了一种用于生产离子交换的微孔硅铝磷酸盐材料的方法，其通过在SAPO-34晶体的表面上产生金属氧化物或金属盐颗粒，随后在500至800℃，优选650至750℃下加热12至72小时的时间，以产生金属阳离子。金属氧化物颗粒或金属盐颗粒通过浸渍或沉淀而形成在SAPO-34晶体的表面上。该方法不同于常规的离子交换，因为实际的离子交换步骤是在去除用于浸渍或沉积的液体之后进行的。该方法要求高温和长的加热时间。该方法可以在干燥或湿润的空气中执行。该方法的变型描述于以下文献中：D.Wang,L.Zhang,J.Li,K.Kamasamudram,W.S.Epling,Catal.Today(2013),DOI 10.1016/j.cattod.2013.11.040和M.Zamadics,X.Chen,L.Kevan,J.Phys.Chem.(1992)5488。与在SAPO晶体表面上产生金属氧化物颗粒不同，H形式的SAPO-34与CuO物理混合，并在800℃加热12小时。在两篇文献中均可以确认Cu离子交换的完成。
专利EP955080公开了用于将Cu、Fe、Co、Mn、Pd、Rh或Pt通过以下方法引入到具有大于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。
我们已观察到：当用金属氧化物和/或金属盐与微孔硅铝磷酸盐的物理混合物进行的固态离子交换是在含有NH3的气氛中进行时，大大改善了金属交换的微孔金属铝磷酸盐材料的制备。氨的存在使得能够在低至250℃的温度下执行固态交换。鉴于以下事实这是令人惊讶的：通常需要600至800℃范围的温度以活化用于SCR反应的Cu-SAPO-34材料。此外，本发明的方法还允许使用低于300℃的温度，其是专利EP955080中公开的用于铝硅酸盐沸石的温度下限，在该温度下通常更容易引入金属离子。
本发明的优点是，SCR活性结晶微孔金属铝磷酸盐材料可以在显著更低的温度下制备，由此降低了在引入金属离子过程中损坏这些材料的风险。
根据上述观察，本发明提供了用于制备金属交换的结晶微孔金属铝磷酸盐或含有金属交换的微孔金属铝磷酸盐材料的混合物的固态离子交换方法，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金属铝磷酸盐起始材料，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至一定温度和持续一定时间，其足以引发和进行金属化合物的离子和结晶微孔材料的离子的固态离子交换；
以及获得金属交换的微孔金属铝磷酸盐材料或含有金属交换的微孔金属铝磷酸盐材料的混合物。
在本发明的一个实施方案中，一种或多种金属铝磷酸盐起始材料含有选自由硅、钛、锡、锌、镁、锰、钴或铁组成的组中的一种或多种金属。
可用的微孔金属铝磷酸盐起始材料可以是具有离子交换能力的任何微孔金属铝磷酸盐材料。
优选地，微孔铝磷酸盐材料中的一部分磷和可能的铝原子被Si替换，以产生硅铝磷酸盐。
优选地，微孔金属铝磷酸盐起始材料具有命名为CHA、AEI、AFI、AEL、AST、AFR、AFO和FAU的晶体结构。这样的材料的已知最好的例子是SAPO-34、SAPO-44和SAPO-18。
在一个实施方案中，微孔金属铝磷酸盐材料是H或NH4形式。
在另一个实施方案中，微孔金属铝磷酸盐起始材料含有有机结构导向剂。
还在另一个实施方案中，用于制备金属交换的结晶微孔金属铝磷酸盐的干混合物中的金属化合物为金属氧化物、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。
可用于这些金属化合物中的金属包括Fe、Cu和Co或其组合。
在一个实施方案中，这些金属选自Fe和/或Cu。
在一个实施方案中，金属化合物为CuO或Cu2O或其混合物。
另一个实施方案是使所述混合物暴露于含有氨的气氛，其中氨在气氛中的含量为1至5000体积ppm。
再一个实施方案是使所述混合物暴露于含有氨的气氛，其中氧在气氛中的含量为10体积％或更少。
另一个实施方案是使所述混合物暴露于含有氨的气氛，其中水在气氛中的含量为5体积％或更少。
在一个优选的实施方案中，将混合物在含有氨的气氛中加热到低于300℃的温度。
还在一个优选的实施方案中，将混合物在含有氨的气氛中加热到100℃至250℃的温度。
本发明的再一个方面是金属交换的微孔金属铝磷酸盐材料或金属交换的微孔金属铝磷酸盐材料的混合物，其是通过根据本发明的上述公开的任一方面和实施方案的方法所获得的。本发明的再一个方面是通过用还原剂进行选择性催化还原而从废气中去除氮氧化物的方法，该方法包括使废气与包含通过根据本发明的任一上述实施方案的方法所获得的金属交换的结晶微孔金属铝磷酸盐材料或金属交换的结晶微孔金属铝磷酸盐材料的混合物的催化剂接触。
优选的还原剂包括氨或其前体或烃。
实施例1
通过将CuO和H-SAPO-34材料混合至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N2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160℃并暴露于在N2中的500ppm的NO、533ppm的NH3、5体积％的H2O和10体积％的O2的气体混合物。然后使温度逐步升高至180、200和220℃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。
表1中给出了在不同温度下测量的NO转化率。注意，SCR活性的SAPO-34材料在添加Cu之后未再加热至高于250℃。该实施例表明，本发明的方法提供了生产基于SAPO-34的活性催化剂的方法，其不需要在升高的温度(>700℃)下进行活化，而对于常规离子交换的SAPO-34材料则需要高温活化(P.N.R.A.Katerinopoulou,R.R.Tiruvalam,A.Kustov,P.G.Moses,P.Concepcion,A.Corma,ACS Catal.2013,3,2158–2161)。
表1：在500ppm的NH3中在250℃下加热CuO和H-SAPO-34的混合物10小时之后在不同温度下的NOx转化率。
温度(℃) NOx转化率(％)
180 4.8
200 8.0
220 15.0
实施例2
为了比较，通过将CuO和H-SAPO-34材料混合至12.5wt％的CuO含量制备了与实施例1类似的催化剂。将催化剂的样品置于石英U形管反应器中，并在纯的N2气氛中在250℃下加热10小时。加热后，将催化剂冷却至160℃并暴露于在N2中的500ppm的NO、533ppm的NH3、5体积％的H2O和10体积％的O2的气体混合物。然后使温度逐步升高至180、200和220℃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。
表2中给出了在不同温度下测量的NO转化率。在纯的N2中处理CuO和H-SAPO-34的混合物之后所获得的NOx转化率大大低于实施例1中所给出的在500ppm的NH3的存在下进行相当的处理之后所获得的转化率。这表明，对于能够在低温下通过固态离子交换来生产Cu-SAPO-34而言，NH3的存在是至关重要的。由于SCR活性的测量意味着体系暴露于低浓度的氨，所以在测量过程中发生了一些Cu-SAPO-34的形成以及测量了NOx的较低转化率，其完全符合本发明。
表2：仅氮气中在250℃下加热CuO和H-SAPO-34的混合物10小时后在不同温度下的NOx转化率。
温度(℃) NOx转化率(％)
180 1.8
200 1.7
220 3.5
实施例3
该实施例表明，可以通过本发明的方法使用Cu2O在低于300℃下制备用于SCR的活性金属交换的金属铝磷酸盐催化剂。通过在研钵中研磨来制备10wt％的Cu2O与H-SAPO-34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体积％的H2O和10体积％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3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3.在各种不同温度下在NH3中处理5小时后Cu2O+H-SAPO-34混合物的NOx转化率

Claims (15)

1.用于制备金属交换的结晶微孔金属铝磷酸盐或含有金属交换的微孔金属铝磷酸盐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金属铝磷酸盐起始材料，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100℃至250℃的温度和持续一定时间，其足以引发和进行金属化合物的离子和结晶微孔材料的离子的固态离子交换；
以及获得金属交换的微孔金属铝磷酸盐材料或含有金属交换的微孔金属铝磷酸盐材料的混合物，
其中干混合物中的所述一种或多种金属化合物选自由金属氧化物、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，
其中所述一种或多种金属化合物中的金属选自由Fe、Co、Cu组成的组。
2.根据权利要求1所述的方法，其中所述一种或多种金属铝磷酸盐起始材料含有选自由硅、钛、锡、锌、镁、锰、钴或铁组成的组中的一种或多种金属。
3.根据权利要求1或2所述的方法，其中所述一种或多种金属铝磷酸盐起始材料具有CHA、AEI、AFI、AEL、AST、AFR、AFO和FAU的框架代码。
4.根据权利要求1或2所述的方法，其中所述一种或多种金属铝磷酸盐起始材料含有选自由SAPO-34、SAPO-44、SAPO-18或其组合组成的组。
5.根据权利要求1或2所述的方法，其中所述一种或多种微孔金属铝磷酸盐起始材料是H+或NH4 +形式。
6.根据权利要求1或2所述的方法，其中所述一种或多种微孔金属铝磷酸盐起始材料含有有机结构导向剂。
7.根据权利要求1或2所述的方法，其中所述一种或多种金属化合物由Fe和/或Cu的氧化物组成。
8.根据权利要求1或2所述的方法，其中所述一种或金属化合物为Cu(I)氧化物和/或Cu(II)氧化物。
9.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。
10.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体积％或更少。
11.根据权利要求1或2所述的方法，其中所述气氛包含5体积％或更少的水。
12.一种金属交换的微孔金属铝磷酸盐材料或金属交换的微孔金属铝磷酸盐材料的混合物，其是通过权利要求1至11中任一项所述的方法获得的。
13.一种通过用还原剂进行选择性催化还原而从废气中去除氮氧化物的方法，所述方法包括使所述废气与包含通过根据权利要求1至11中任一项所述的方法获得的金属交换的结晶微孔金属铝磷酸盐材料或金属交换的结晶微孔金属铝磷酸盐材料的混合物的催化剂接触。
14.根据权利要求13所述的方法，其中所述还原剂是氨或其前体。
15.根据权利要求13所述的方法，其中所述还原剂包括烃。
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