CN110270342A - 一种铁铈铝氧化物催化剂、制备方法及其应用 - Google Patents
一种铁铈铝氧化物催化剂、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种铁铈铝氧化物催化剂、制备方法及其应用。该催化剂包括γ‑Al2O3载体、活性组分Fe、Ce，所述活性组分以Fe2O3和CeO2的形式存在于该催化剂中，该催化剂中各组分γ‑Al2O3∶Fe2O3∶CeO2的质量比为1∶0.093∶0.199。该催化剂是采用共浸渍法或分步浸渍法，经烘干、焙烧制得，应用于CO+O2反应，表现出较好的催化性能，能将10％‑100％的CO转化为CO2。本发明的催化剂的比表面积大、催化性能优异、原料廉价易得、资源丰富，在机动车尾气CO消除中能耗低、污染小、环境友好，具有广阔的应用前景。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种铁铈铝氧化物催化剂、制备方法及其应用。
背景技术
近年来，随着我国机动车保有量的迅猛增加，给人类的生产、生活带来了极大的便利。但是，由机动车尾气所带来的大气污染问题也给社会生活造成了严重困扰。传统汽车以汽油、柴油等石油资源为燃料，其尾气组成非常复杂，主要包括一氧化碳(CO)、氮氧化物(NOx)、碳氢化合物(CxHy)和固体颗粒物等。这些污染物可能造成温室效应、臭氧层破坏、雾霾以及酸雨等环境问题。同时，部分污染物可直接被人体、动植物吸收，对生态系统造成严重破坏。因此，如何有效控制机动车的尾气污染状况是当今社会的一项重要挑战。从经济性的角度来说，在汽车尾气排放达到欧IV排放标准以后，国际上降低尾气的排放便不再从发动机本身结构等方面采取措施，而是通过采用排气后处理的方式也就是机外净化技术来降低尾气的排放量。因而开发高效、经济的机动车尾气后处理技术是实现尾气催化消除的必然选择。对于CO的催化消除，商业上使用的催化剂主要是以Au、Pt、Pd、Rh等贵金属为活性组分的催化剂，此类催化剂虽然性能优异，但是也存在价格高、储量少等缺点。因此，越来越多的研究把目光集中到非贵金属催化剂的研发上来。
Fe2O3是一种常见的过渡态非贵金属氧化物，具有价廉、无毒、且储量大等特点。并且，铁存在+2、+3和+(3-δ)等多种价态，是一种良好的氧化还原剂。3d5的轨道构型也容易接受CO的孤对电子，有利于CO分子在其表面的吸附。另外，还有研究指出，Fe2O3本身存在许多缺陷位，包括阳离子缺陷、阴离子缺陷以及间隙缺陷等，这些缺陷位点有利于氧空位的产生，从而可以更加容易的活化O2，促进CO氧化反应的进行。
CeO2凭借其优异的储释氧性能以及Ce3+/Ce4+氧化还原电对，广泛应用于CO氧化反应中。研究发现，在Fe2O3-CeO2催化剂中，通过Fe3+/Fe2+和Ce3+/Ce4+双电子对之间的电子转移，可以产生Fe-O-Ce间的相互作用。且在CeO2中掺杂Fe离子后，可以显著提升CeO2的CO氧化性能，这主要是因为掺杂后的催化剂表现出更小的晶粒尺寸、更强的晶格应力、较好的氧化还原能力以及更为丰富的表面氧空位浓度等。
刚性载体γ-Al2O3比表面积大，孔隙构造发达，能使所负载的活性组分高度分散，借助载体的空位阻隔作用，可防止活性组分微粒在使用过程中烧结长大。
目前具有优异CO氧化反应性能的FeCe/Al催化剂还未见报道。
发明内容
发明目的：针对现有技术的不足，本发明的目的是提供一种铁铈铝氧化物催化剂，原料廉价易得、资源丰富，所得催化剂的比表面积大、催化性能优异。本发明的另一目的是提供铁铈铝氧化物催化剂的制备方法，简便快捷、可大规模生产。本发明的再一目的是提供上述催化剂在CO氧化反应中的应用，催化性能优异，能耗低、污染小、环境友好，在机动车尾气CO消除中的应用前景广阔。
技术方案：为了实现上述发明目的，本发明采用的技术方案为：
一种铁铈铝氧化物催化剂，包括γ-Al2O3载体、活性组分Fe、Ce，所述活性组分以Fe2O3和CeO2的形式存在于该催化剂中。
催化剂中各组分γ-Al2O3∶Fe2O3∶CeO2的质量比为1∶0.093∶0.199。
铁铈铝氧化物催化剂的制备方法，是采取共浸渍法，经烘干、焙烧制得，具体步骤如下：将γ-Al2O3载体、Fe(NO3)·9H2O和Ce(NO3)·6H2O溶解于去离子水中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，500℃空气气氛下焙烧4h。
γ-Al2O3载体、Fe(NO3)·9H2O、Ce(NO3)·6H2O的质量比为1∶0.202∶0.503。
铁铈铝氧化物催化剂的制备方法，是采取分步浸渍法，经烘干、焙烧制得，具体步骤如下：称取γ-Al2O3载体分散于去离子水中，再称取Ce(NO3)·6H2O溶解于上述溶液中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，把得到的固体研磨、500℃空气气氛下焙烧4h，得到CeO2/γ-Al2O3，利用浸渍法负载相同量的Fe(NO3)·9H2O，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，500℃空气气氛下焙烧4h。
γ-Al2O3载体、Ce(NO3)·6H2O的质量比为1∶0.503。
催化剂在CO氧化反应中的应用。
催化剂在N2气氛下200℃吹扫1h，催化剂与CO、O2、N2的气流按质量浓度比进行反应。
催化剂、CO、O2、N2的质量浓度比为50mg∶1.6vol％∶20.8vol％∶77.6vol％，气流空速为30000mL·g-1·h-1。
该应用将10％-100％的CO转化为CO2。
有益效果：与现有技术相比，本发明采用共浸渍法或分步浸渍法制备铁铈铝氧化物催化剂，并将其应用于CO+O2反应，表现出较好的催化性能，具体具有以下的技术优势：
1)制备所得催化剂的比表面积大、催化性能优异；
2)原料廉价易得、资源丰富；
3)方法简便快捷、可大规模生产；
4)能耗低、污染小、环境友好；
5)在机动车尾气CO消除中的应用前景广阔。
附图说明
图1是铁铈铝氧化物催化剂的XRD结果图；
图2是铁铈铝氧化物催化剂的EPR结果图；
图3是铁铈铝氧化物催化剂的H2-TPR结果图；
图4是铁铈铝氧化物催化剂的反应活性图。
具体实施方式
下面结合具体实施例进一步说明本发明，但这些实例并不用来限制本发明。下述实施例中所使用的实验方法如无特殊说明，均为常规方法。下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1共浸渍法制备Fe2O3-CeO2/γ-Al2O3
把质量比为1∶0.202∶0.503的γ-Al2O3载体和Fe(NO3)·9H2O及Ce(NO3)·6H2O溶解于去离子水中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，500℃空气气氛下焙烧4h。得到Fe2O3-CeO2/γ-Al2O3样品，样品简写为：FeCe/Al-CI。
实施例2分步浸渍法制备Fe2O3-CeO2/γ-Al2O3
按质量比为1∶0.202或1∶0.503分别称取γ-Al2O3载体分散于适量的去离子水中，再称取一定量的Fe(NO3)·9H2O或Ce(NO3)·6H2O溶解于上述溶液中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜。最后，把得到的固体研磨、500℃空气气氛下焙烧4h，得到Fe2O3/γ-Al2O3或CeO2/γ-Al2O3样品，简写为：Fe/Al或Ce/Al。
制备Ce/Al催化剂作为载体，再利用浸渍法负载相同量的Fe(NO3)·9H2O，制备条件与实施例1一致。样品简写为：FeCe/Al-SI。
对比样1：分别称取Fe/Al、FeCe/Al-CI、FeCe/Al-SI置于20mL硝酸溶液中(50％)，在室温下搅拌48h，抽滤，洗涤，烘干过夜，样品标记为：Fe/Al-H、FeCe/Al-CI-H和FeCe/Al-SI-H。
对比样2：取相同质量的Fe/Al和Ce/Al样品混合均匀，研磨、压片，记作Fe/Al+Ce/Al。
实施例3铁铈铝氧化物催化剂表征
1)X射线衍射(XRD)分析结果如图1所示，Fe物种主要是以分散态的形式存在。在含Ce物种的催化剂中，均出现了晶相CeO2的特征峰，表明CeO2在催化剂中是以晶相形式存在的。且FeCe/Al-CI样品中CeO2的晶相衍射峰强度明显弱于Ce/Al及FeCe/Al-SI样品，这可能是Fe物种与Ce物种的相互作用，导致CeO2分散度提升、颗粒减小。
XRD主要在Philips X’pert Pro型衍射仪上进行，采用Ni滤波片和Cu靶Kα辐射源(波长为0.15418nm)。X射线灯管的工作电压为40kV，工作电流为40mA。强度数据采集范围为2θ＝10-80°，扫描速度为10°min-1，步长为0.02°。
2)电子顺磁共振(EPR)分析结果如图2所示，对于g＝2.6-2.3处的宽峰，在加入Ce以后，峰强度发生了明显的变化：Fe/Al＞FeCe/Al-CI＞FeCe/Al-SI。说明Ce的添加可以减少Fe/Al样品中团聚态Fe3+物种的含量，促进Fe物种的分散。而且，采用分步浸渍法制备的FeCe/Al-SI样品较采用共浸渍方法制备的FeCe/Al-CI更有利于Fe物种的分散。
电子顺磁共振在德国Bruker公司EMX-10/12仪器上进行，仪器调制频率为100kHz，测试温度为室温。
3)H2-程序升温还原分析结果如图3所示，可以发现FeCe/Al样品的总峰面积远远大于Fe/Al样品，说明Ce的添加可以提高催化剂的低温还原性能，Fe-O-Ce间的协同作用促进了CeO2的还原。对比各还原峰的面积大小，可以发现FeCe/Al-SI的孤立态物种还原峰的面积要大于FeCe/Al-CI中孤立态铁物种的峰面积，说明FeCe/Al-SI中有更多的孤立Fe物种。
H2-TPR在自组装的TPR仪器上进行。称取25mg催化剂置于U型石英管中经高纯N2在200℃下吹扫1h；冷却至室温后切换至H2-Ar混合气(H2的体积百分数为7.0％，流速为70ml·min-1)从室温开始采集数据直到目标温度，升温速率为10℃·min-1。检测器为热导池检测器(TCD)。
实施例4铁铈铝氧化物催化剂的活性
将上述制备的催化剂应用于CO+O2反应，具体反应条件如下：催化剂的CO+O2性能评价在固定床反应器上进行，使用石英微反应器，催化剂用量为50mg。反应气的体积组成是：CO 1.6vol％，O2 20.8vol％，N2 77.6vol％，气体空速为30000mL·g-1.h-1。测试前，样品首先在N2气氛下200℃吹扫1h。冷却至室温后切换至反应气开始反应。产物经气相色谱仪分离后由热导检测器检测。
CO转化率由如下公式计算得到：
如图4所示，在Fe/Al催化剂中添加Ce后，FeCe/Al的反应性能得到了明显提升。对比机械混合的Fe/Al+Ce/Al样品，说明Fe与Ce物种的相互作用是导致FeCe/Al性能提升的主要因素。对比不同Ce添加方式制备的FeCe/Al样品，可以发现FeCe/Al-CI拥有更好的催化性能。而酸洗后样品的低温CO转化率急剧下降。
Claims (10)
1.一种铁铈铝氧化物催化剂，其特征在于，所述催化剂包括γ-Al2O3载体、活性组分Fe、Ce，所述活性组分以Fe2O3和CeO2的形式存在于该催化剂中。
2.根据权利要求1所述的铁铈铝氧化物催化剂，其特征在于，所述催化剂中各组分γ-Al2O3∶Fe2O3∶CeO2的质量比为1∶0.093∶0.199。
3.权利要求1所述的铁铈铝氧化物催化剂的制备方法，其特征在于，所述催化剂是采取共浸渍法，经烘干、焙烧制得，具体步骤如下：将γ-Al2O3载体、Fe(NO3)·9H2O和Ce(NO3)·6H2O溶解于去离子水中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，500℃空气气氛下焙烧4h。
4.根据权利要求3所述的制备方法，其特征在于，γ-Al2O3载体、Fe(NO3)·9H2O、Ce(NO3)·6H2O的质量比为1∶0.202∶0.503。
5.权利要求1所述的铁铈铝氧化物催化剂的制备方法，其特征在于，所述催化剂是采取分步浸渍法，经烘干、焙烧制得，具体步骤如下：称取γ-Al2O3载体分散于去离子水中，再称取Ce(NO3)·6H2O溶解于上述溶液中，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，把得到的固体研磨、500℃空气气氛下焙烧4h，得到CeO2/γ-Al2O3，利用浸渍法负载相同量的Fe(NO3)·9H2O，搅拌2h，100℃油浴蒸干，并置于烘箱中110℃干燥过夜，500℃空气气氛下焙烧4h。
6.根据权利要求5所述的制备方法，其特征在于，γ-Al2O3载体、Ce(NO3)·6H2O的质量比为1∶0.503。
7.权利要求1所述的催化剂在CO氧化反应中的应用。
8.根据权利要求7所述的应用，其特征在于，包括以下步骤：催化剂在N2气氛下200℃吹扫1h，催化剂与CO、O2、N2的气流按质量浓度比进行反应。
9.根据权利要求8所述的应用，其特征在于，催化剂、CO、O2、N2的质量浓度比为50mg∶1.6vo1％∶20.8vol％∶77.6vol％，气流空速为30000mL·g-1·h-1。
10.根据权利要求所述的8应用，其特征在于，该应用将10％-100％的CO转化为CO2。
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