铈铬基氨选择性催化还原氮氧化物催化剂的研究
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摘要
氮氧化物能够引起酸雨和光化学烟雾,已成为大气环境的主要污染物之一。如何控制和治理日益严重的氮氧化物污染已经成为国际上研究的热点。氨气选择性催化还原氮氧化物技术(SCR)是目前治理氮氧化物应用最广泛的技术,高活性的SCR催化剂一直是人们研究的焦点。复合金属氧化物由于其特殊的晶体结构和较高的氧化还原能力越来越受到人们关注,在SCR领域具有广阔的应用前景。
CeO_2由于其独特的氧化还原能力和酸碱性能,作为助催化剂或活性组分广泛地应用于催化领域。CeO_2晶格中部分Ce4+被尺寸较小的低价态离子取代形成的固溶体,显示出更高的热稳定性、储氧能力和催化性能,对CeO_2的掺杂改性引起了研究者和产业界的广泛关注。而Cr作为变价元素,具有优异的氧化还原能力,因此将Cr掺入CeO_2中可能会有意想不到的NOx去除效果。
本文以氨水为沉淀剂采用共沉淀法制备了铈铬复合氧化物,利用N2吸附/脱附、X射线衍射(XRD)、透射电子显微镜(TEM)对合成样品的晶相、孔结构性质、形貌进行表征;利用拉曼光谱(Raman)、X射线光电子能谱(XPS)等对合成样品的表面特性进行了表征。利用氢气程序升温还原(H2-TPR)技术对催化剂的还原性能进行了研究。分析了Cr的含量、焙烧温度对合成铈铬复合氧化物结构以及形貌的影响。利用固定床反应器,采用NOx分析仪和四极质谱,对复合氧化物的氮氧化物的选择性催化还原性能进行了研究。
研究结果表明,对于未焙烧样品,Cr掺杂的复合氧化物与CeO_2相比具有更高的比表面积;TEM结果显示,Cr的掺杂使得复合氧化物的形貌发生显著变化,当Cr含量为1-5 at.%时,样品呈现长约60-150 nm、直径为15-20 nm的棒状结构,进一步增加Cr含量,纳米棒的比例逐渐降低,当Cr的掺杂量达到20 at.%时,已经观察不到纳米棒的存在。
焙烧后样品的表征结果显示,当Cr掺杂量≤3 at.%时,复合氧化物抗烧结能力比CeO_2有了明显提高,进一步增加Cr的掺杂量,复合氧化物的比表面积衰减幅度变大,Cr含量为20 at.%样品的比表面积衰减了75 %;XRD结果表明,650℃焙烧后Cr掺杂量20 at.%样品析出了Cr2O3的晶相。XPS和Raman结果证实,在铈铬复合氧化物中Ce主要是以Ce4+形式存在,同时也有少量的Ce~(3+)存在;而Cr是以Cr6+和Cr~(3+)两种形式存在的,并且主要富集在催化剂表面。由于Ce~(3+)以及Cr~(3+)、Cr6+的存在,致使铈铬复合氧化物的氧空位数较之CeO_2明显增加。
H2-TPR测试结果表明,Cr的掺杂提高了复合氧化物的氧化还原性能。结合表征结果证实复合氧化物中存在两种Cr6+物种:可溶性的Cr6+以及嫁接型Cr6+,前者较后者更容易被还原。而嫁接型Cr6+与Ce4+之间存在相互作用,一方面限制了Cr6+的还原,另一方面又促进了Ce4+的还原,使得复合氧化物的氧化还原能力比CeO_2有了显著增强。
氨选择性催化还原氮氧化物的性能测试结果表明,Cr的掺杂对复合氧化物的活性有明显的促进作用,结合表征结果推断Cr的掺杂提高了复合氧化物的氧化还原性能,并产生了更多的氧空位,有利于NO在催化剂上的预氧化,促进了催化反应的进行。虽然400℃焙烧样品相比650℃有更大的比表面积,但是反应出来的活性数据却显示两者相差不大,这说明对于NH3-SCR反应体系,比表面积是影响活性的重要因素,但并不是唯一因素。比较了不同合成方法合成的Ce90Cr10样品的活性,结果显示大的比表面积使得富集在催化剂表面的Cr6+物种分散更均匀,与反应气氛接触时能够提供更多的活性点,有利于NOx的去除,同时较小的孔径可能抑制了NOx的去除,SCR反应本质上是一个气固反应,气体的扩散与吸附会受到孔径大小的影响,大的孔径往往能够展现出高的活性。
Nitrogen oxides are main atmospheric pollutants, which can cause acid rain and photochemical smog. The NOx control technology has been a research focus in the international environmental protection field. Among the present technologies of NOx control, the selective catalytic reduction (SCR) with NH3 is the most widely used treatment technology. The development of an SCR catalyst with high activity has been the key of SCR technology. Because of the unique crystal structure and high redox properties, the composite metal oxides are paid more and more attention, which have broad application in the domain of deNOx.
The wide application of cerium oxide either as a promoter or as an active catalyst is due to its unique redox and acid–base properties. The doping of undersized lower valence ions to form a ceria-based solid solution can enhance the thermal stability, oxygen storage capacity, and catalytic activities. Cr is an elements with variable valences and has excellent redox ability, therefore Cr doped CeO_2 for deNOx is intriguing.
In this work, Ce-Cr composite oxides were prepared by co-precipitation method using ammonia as the precipitation agent and characterized by N2 adsorption/desorption, X-ray diffraction(XRD), transmission electron microscopy (TEM), raman spectra (Raman), X-ray photoelectron spectra (XPS). Temperature programmed reduction of H2 (H2-TPR) tests were employed to determine the redox properties. The effects of Cr contents and calcination temperatures on crystal phase and surface properties were investigated. The NH3-SCR was performed on a fixed bed reactor to study the catalytic activity.
Before calcinations, the Ce-Cr composites had a larger specific surface area than that of CeO_2. TEM results show that the samples with 1-5 (molar content) of Cr doping show nanorod morphologies, which coexists with some nanoscaled particles. The length of the nanorods is about 60-150 nm and the width is 15-20 nm. With the increase in Cr, the yield of nanorods reduced gradually. When Cr content is 20 at%, no nanorods were observed. After calcinations, the samples with the Cr content less that 3 at% show improved anti-sintering ability than that of CeO_2. Further increase in Cr results in the decrease in the surface area compared with CeO_2. The Cr2O3 phase was observed for the 20 at.% Cr doped sample. Ce is mainly in + 4 valence, but there are a number of Ce~(3+) simultaneously. However, Cr is mainly segregated to the surface in two forms (Cr6+ and Cr~(3+)). The presence of Ce~(3+), Cr~(3+) and Cr6+ in mixed oxides results in an increased in concentrations of oxygen vacancies compared with pure CeO_2.
The H2-TPR results show that the redox properties are enhanced by the doping of Cr. There may be two kinds of Ce6+ species in the mixed oxides. Hydrogen consumption peak at the lower temperature can be attributed to the reduction of soluble Ce6+, and the peak at the higher temperature is caused by the grafted Cr6+, which is formed by the interaction between Ce6+ and Ce4+. The results of catalytic activities for NH3-SCR show that the addition of Cr improved the catalytic performance of the composite oxides. Ce90Cr10 shows the highest activity. Although the samples calcined at 400℃had a higher surface area than that at 650℃, the activity shows little difference.
The specific surface area is an important factor for the NH3-SCR reaction system, but it is not the only one. SCR reaction is essentially a gas-solid reaction, the diffusion and adsorption of gases will be affected by pore sizes. The larger pore size can often results in the higher activity.
CeO_2由于其独特的氧化还原能力和酸碱性能,作为助催化剂或活性组分广泛地应用于催化领域。CeO_2晶格中部分Ce4+被尺寸较小的低价态离子取代形成的固溶体,显示出更高的热稳定性、储氧能力和催化性能,对CeO_2的掺杂改性引起了研究者和产业界的广泛关注。而Cr作为变价元素,具有优异的氧化还原能力,因此将Cr掺入CeO_2中可能会有意想不到的NOx去除效果。
本文以氨水为沉淀剂采用共沉淀法制备了铈铬复合氧化物,利用N2吸附/脱附、X射线衍射(XRD)、透射电子显微镜(TEM)对合成样品的晶相、孔结构性质、形貌进行表征;利用拉曼光谱(Raman)、X射线光电子能谱(XPS)等对合成样品的表面特性进行了表征。利用氢气程序升温还原(H2-TPR)技术对催化剂的还原性能进行了研究。分析了Cr的含量、焙烧温度对合成铈铬复合氧化物结构以及形貌的影响。利用固定床反应器,采用NOx分析仪和四极质谱,对复合氧化物的氮氧化物的选择性催化还原性能进行了研究。
研究结果表明,对于未焙烧样品,Cr掺杂的复合氧化物与CeO_2相比具有更高的比表面积;TEM结果显示,Cr的掺杂使得复合氧化物的形貌发生显著变化,当Cr含量为1-5 at.%时,样品呈现长约60-150 nm、直径为15-20 nm的棒状结构,进一步增加Cr含量,纳米棒的比例逐渐降低,当Cr的掺杂量达到20 at.%时,已经观察不到纳米棒的存在。
焙烧后样品的表征结果显示,当Cr掺杂量≤3 at.%时,复合氧化物抗烧结能力比CeO_2有了明显提高,进一步增加Cr的掺杂量,复合氧化物的比表面积衰减幅度变大,Cr含量为20 at.%样品的比表面积衰减了75 %;XRD结果表明,650℃焙烧后Cr掺杂量20 at.%样品析出了Cr2O3的晶相。XPS和Raman结果证实,在铈铬复合氧化物中Ce主要是以Ce4+形式存在,同时也有少量的Ce~(3+)存在;而Cr是以Cr6+和Cr~(3+)两种形式存在的,并且主要富集在催化剂表面。由于Ce~(3+)以及Cr~(3+)、Cr6+的存在,致使铈铬复合氧化物的氧空位数较之CeO_2明显增加。
H2-TPR测试结果表明,Cr的掺杂提高了复合氧化物的氧化还原性能。结合表征结果证实复合氧化物中存在两种Cr6+物种:可溶性的Cr6+以及嫁接型Cr6+,前者较后者更容易被还原。而嫁接型Cr6+与Ce4+之间存在相互作用,一方面限制了Cr6+的还原,另一方面又促进了Ce4+的还原,使得复合氧化物的氧化还原能力比CeO_2有了显著增强。
氨选择性催化还原氮氧化物的性能测试结果表明,Cr的掺杂对复合氧化物的活性有明显的促进作用,结合表征结果推断Cr的掺杂提高了复合氧化物的氧化还原性能,并产生了更多的氧空位,有利于NO在催化剂上的预氧化,促进了催化反应的进行。虽然400℃焙烧样品相比650℃有更大的比表面积,但是反应出来的活性数据却显示两者相差不大,这说明对于NH3-SCR反应体系,比表面积是影响活性的重要因素,但并不是唯一因素。比较了不同合成方法合成的Ce90Cr10样品的活性,结果显示大的比表面积使得富集在催化剂表面的Cr6+物种分散更均匀,与反应气氛接触时能够提供更多的活性点,有利于NOx的去除,同时较小的孔径可能抑制了NOx的去除,SCR反应本质上是一个气固反应,气体的扩散与吸附会受到孔径大小的影响,大的孔径往往能够展现出高的活性。
Nitrogen oxides are main atmospheric pollutants, which can cause acid rain and photochemical smog. The NOx control technology has been a research focus in the international environmental protection field. Among the present technologies of NOx control, the selective catalytic reduction (SCR) with NH3 is the most widely used treatment technology. The development of an SCR catalyst with high activity has been the key of SCR technology. Because of the unique crystal structure and high redox properties, the composite metal oxides are paid more and more attention, which have broad application in the domain of deNOx.
The wide application of cerium oxide either as a promoter or as an active catalyst is due to its unique redox and acid–base properties. The doping of undersized lower valence ions to form a ceria-based solid solution can enhance the thermal stability, oxygen storage capacity, and catalytic activities. Cr is an elements with variable valences and has excellent redox ability, therefore Cr doped CeO_2 for deNOx is intriguing.
In this work, Ce-Cr composite oxides were prepared by co-precipitation method using ammonia as the precipitation agent and characterized by N2 adsorption/desorption, X-ray diffraction(XRD), transmission electron microscopy (TEM), raman spectra (Raman), X-ray photoelectron spectra (XPS). Temperature programmed reduction of H2 (H2-TPR) tests were employed to determine the redox properties. The effects of Cr contents and calcination temperatures on crystal phase and surface properties were investigated. The NH3-SCR was performed on a fixed bed reactor to study the catalytic activity.
Before calcinations, the Ce-Cr composites had a larger specific surface area than that of CeO_2. TEM results show that the samples with 1-5 (molar content) of Cr doping show nanorod morphologies, which coexists with some nanoscaled particles. The length of the nanorods is about 60-150 nm and the width is 15-20 nm. With the increase in Cr, the yield of nanorods reduced gradually. When Cr content is 20 at%, no nanorods were observed. After calcinations, the samples with the Cr content less that 3 at% show improved anti-sintering ability than that of CeO_2. Further increase in Cr results in the decrease in the surface area compared with CeO_2. The Cr2O3 phase was observed for the 20 at.% Cr doped sample. Ce is mainly in + 4 valence, but there are a number of Ce~(3+) simultaneously. However, Cr is mainly segregated to the surface in two forms (Cr6+ and Cr~(3+)). The presence of Ce~(3+), Cr~(3+) and Cr6+ in mixed oxides results in an increased in concentrations of oxygen vacancies compared with pure CeO_2.
The H2-TPR results show that the redox properties are enhanced by the doping of Cr. There may be two kinds of Ce6+ species in the mixed oxides. Hydrogen consumption peak at the lower temperature can be attributed to the reduction of soluble Ce6+, and the peak at the higher temperature is caused by the grafted Cr6+, which is formed by the interaction between Ce6+ and Ce4+. The results of catalytic activities for NH3-SCR show that the addition of Cr improved the catalytic performance of the composite oxides. Ce90Cr10 shows the highest activity. Although the samples calcined at 400℃had a higher surface area than that at 650℃, the activity shows little difference.
The specific surface area is an important factor for the NH3-SCR reaction system, but it is not the only one. SCR reaction is essentially a gas-solid reaction, the diffusion and adsorption of gases will be affected by pore sizes. The larger pore size can often results in the higher activity.
引文
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