涂层组分对堇青石脱硝催化剂性能的影响

为了探究涂层组分对整体式低温选择性催化还原（SCR）脱硝催化剂性能的影响,本文使用锰氧化物（MnO _x ）、氧化物涂层（TiO₂、SiO₂及Al₂O₃）、堇青石（CC）基体制备整体式涂层催化剂,考察催化剂牢固度以及脱硝活性。结果表明：在200℃ 时,对于MnO _x /Al₂O₃/CC催化剂,MnO _x 负载率为6%（质量分数）时脱硝效率最高为95%;对于MnO _x /TiO₂/CC,负载率为6%~12%时脱硝效率相差不大,为75%左右;对于MnO _x /SiO₂/CC,负载率12%时脱硝效率80%。样品牢固度排列顺序如下：MnO _x /Al₂O₃/CC > MnO _x /SiO₂/CC > MnO _x / TiO₂ /CC。通过BET、SEM、TG、Raman、H₂-TPR等测试与分析方法发现：影响催化剂性能的因素主要为活性组分MnO _x 状态以及载体性能的差异。Al₂O₃涂层比表面积适中,作为载体活性好;SiO₂涂层虽然比表面积大、牢固度好,但作为载体活性差;TiO₂作为涂层比表面积较小,溶胶中溶剂挥发快使得涂层表面不均匀。     

Comparison study of Na poisoning effect on copper-based chabazite micropore catalysts for NH3-SCR reaction

Using wet impregnation method to mimic alkali metal poison of ammonia-selective catalytic reduction (NH₃-SCR) catalysts, Cu-based micropore zeolites Cu/SSZ-13 and Cu/SAPO-34 with different Na contents(mass fraction) were prepared, and the Na poisoning mechanism on them was studied. The results show that the externally introduced Na ions can severely affect the NH₃-SCR catalytic activity of the two catalysts, resulting in the collapse of the crystal structure of the catalyst, the decrease of acidity and the reduction of active species. In detail, when Na content was less than 1.82%, Cu/SAPO-34 has higher resistance of Na ions than Cu/SZZ-13; while when Na> 3.48%, Cu/SAPO-34 catalysts almost deactivated thoroughly. By structural characterization (BET, XRD and SEM) and acidity characterization (DRIFTS, NH₃-TPD and H₂-TPR), it was found that with Na poisoning deeper and deeper, Cu/SSZ-13 took a gradual style of the structural destruction, but Cu/SAPO-34 adopted a sudden way. Studies on the mechanism of Na poisoning show that the decrease of acid sites is the main reason for the decrease of SCR activity of Cu/SSZ-13, and the structural collapse is the main reason for the decrease of SCR activity of Cu/SAPO-34.     

基于NH3-SCR反应铜基小孔分子筛催化剂Na中毒对比研究

以浸渍法模拟碱金属中毒NH₃-SCR催化剂过程,制备不同Na含量（质量分数）的铜基小孔分子筛Cu/SSZ-13和Cu/SAPO-34,对比研究了二者的碱金属中毒机理。结果表明,外引Na离子均可严重影响两种催化剂的NH₃-SCR催化活性,造成催化剂的晶相结构坍塌,酸性量减少,活性物种减少。不同的是,Na引入量较低（<1.82%）时,Cu/SAPO-34比Cu/SSZ-13具有更强的Na离子耐受性,而当Na含量高于3.48%时,Cu/SAPO-34几乎完全丧失NH₃-SCR催化活性。通过催化剂的结构表征（BET、XRD和SEM）和酸性位表征（DRIFTS、NH₃-TPD和H₂-TPR）,研究表明随着Na中毒程度的加深,Cu/SSZ-13的结构破坏是渐变式的,而Cu/SAPO-34的结构破坏是突变式的;Na中毒的机理研究表明,酸性位的减少是Cu/SSZ-13的SCR活性下降的主导原因,结构坍塌是Cu/SAPO-34的SCR活性下降的主导原因。     

Fe-BEA Zeolite Catalysts for NH3-SCR of NOx

Iron-containing zeolites are known to be promising catalysts for the NH₃-SCR reaction. Here, we will investigate the catalytic activity of iron-based BEA catalysts, which was found to exhibit improved activities compared to previously described iron-containing zeolite catalysts, such as ZSM-5 and ZSM-12. Series of Fe-BEA zeolite catalysts were prepared using a range of different preparation methods. Furthermore, we found that an iron concentration around 3 wt% on BEA showed a small optimum in SCR activity compared to the other iron loadings studied.     

Cu/SSZ-13催化剂脱硝活性中心与催化性能构效关系的研究

NH₃选择性催化还原NO_x（NH₃-SCR）是目前最有应用前景的柴油车尾气净化技术,该技术的核心是开发具备优异催化性能的催化剂。以具有菱沸石（chabazite,CHA）结构的小孔分子筛SSZ-13为载体制备的Cu/SSZ-13催化剂,因具有优异的催化性能和水热稳定性能而受到广泛关注。制备了系列Cu_x/SSZ-13催化剂,并通过CO原位漫反射红外光谱（DRIFT）和H₂-TPR等方法能够确定具有高催化活性的铜离子在SSZ-13分子筛上的落位和存在状态。CO红外吸附实验发现,采用Cu(NO₃)₂水溶液离子交换法制备的Cu/SSZ-13催化剂上存在多种落位的Cu⁺活性中心。在较低的Cu⁺交换度条件下,Cu⁺优先落位于SSZ-13分子筛的八元环位置,随着交换度的提高,Cu⁺开始落位于SSZ-13分子筛双六元环的位置。H₂-TPR结果表明Cu_x/SSZ-13催化剂上也存在大量落位在八元环位置不稳定的Cu²⁺,这些Cu²⁺很容易被还原为Cu⁺。Cu_x/SSZ-13催化剂经800℃水蒸气连续老化16 h,分子筛骨架崩塌程度随着Cu含量的增加而提高,骨架铝的脱除,导致Cu物种发生团聚,而第二金属Ce元素的引入能够在一定程度上提高Cu/SSZ-13的水热稳定性。催化剂构效关系研究表明,具有一定量稳定存在的Cu⁺,并且拥有大量不稳定存在Cu²⁺的催化剂具有较宽温度范围的脱硝性能。     

焙烧程序对一步合成Cu-SSZ-13催化剂NH3-SCR性能的影响

焙烧程序影响一步合成法制备Cu-SSZ-13催化剂中Cu物种的种类及分布,是影响催化剂在NH₃选择性催化还原（NH₃-SCR）氮氧化物反应中催化性能的重要因素。为研究焙烧程序对该方法制备Cu-SSZ-13催化剂性能的影响,采用不同的焙烧温度及升温速率制备Cu-SSZ-13催化剂,并考察各催化剂的催化活性、水热稳定性及活性物种形态。结果表明焙烧温度不改变催化剂的晶型结构,但影响催化剂的活性物种形态及稳定性。当焙烧温度为600℃时,催化剂中Cu物种全部为孤立的Cu²⁺,并具有极高的稳定性,催化剂具有最佳的活性及水热稳定性。固定焙烧温度为600℃,随升温速率的提高,催化剂活性及水热稳定性表现出下降趋势,考虑经济成本,最佳的升温速率应为1℃/min。因此,以1℃/min的升温速率升至600℃焙烧6h是一步合成法制备Cu-SSZ-13催化剂的最佳焙烧程序,所得催化剂具备优异的NH₃-SCR活性和水热稳定性。     

Combined use of a mass-spectrometer and a UV analyzer in the dynamic study of NH3-SCR for diesel exhaust aftertreatment

A mass spectrometer (MS) and a novel UV analyzer were coupled in the experimental study of the transient Selective Catalytic Reduction (SCR) reactivity, aimed at the development of a dynamic numerical model of SCR converters for the selective reduction of NO _x in Diesel exhausts. Their parallel use revealed an effective method for the understanding of key elements in the SCR reaction mechanism under real operating conditions.     

A general and inherent strategy to improve the water tolerance of low temperature NH3-SCR catalysts via trace SiO2 deposition

Water tolerance is an important topic for low temperature NH₃-SCR, because of the inevitable deactivation of the catalyst in the presence of water. In this work, it was found that by depositing trace SiO₂ onto the surface of Mn_0.2Ti_0.8O₂ catalyst, the catalysts displayed enhanced water-tolerance with no compromise of its initial activity. Furthermore, NH₃-TPD, H₂-TPR, and XPS results indicated that deposition of SiO₂ tuned the pore sizes of the catalysts without modifying their chemical properties, and controlled the inherent capillarity property that led to the improved anti-water performance. This result sheds light on the rational design of NH₃-SCR catalysts with enhanced water-tolerance.     

掺杂元素对Mn基催化剂SCR性能及抗硫性能的影响

采用溶胶凝胶法制备M-Mn/TiO₂催化剂,M=Fe、Ce、Ni、Sm、Cu,考察掺杂元素对催化剂SCR性能和抗硫性能的影响,并采用XRD、H₂-TPR表征手段考察掺杂组分对催化剂性质的影响。结果表明,掺杂金属元素后,催化剂的晶粒尺寸和还原性能发生变化,表现为Fe、Ni的掺杂明显降低催化剂粒径尺寸而Ce、Sm、Cu的掺杂增加了粒径尺寸;Cu和Ni的掺杂有利于提高催化剂的还原性能。SCR实验结果表明,Cu、Sm的掺杂在整个反应温度区间内都会抑制催化剂脱硝活性,而Fe、Ni、Ce的掺杂主要抑制低温活性,在高温阶段则会促进反应的进行。掺杂金属元素后催化剂T₈₀活性窗口顺序为：Fe-Mn/TiO₂＞Ni-Mn/TiO₂＞Ce-Mn/TiO₂≈Mn/TiO₂＞Sm-Mn/TiO₂＞Cu-Mn/TiO₂。Sm-Mn/TiO₂和Ce-Mn/TiO₂能保持与Mn/TiO₂基本相似的抗硫性能,但掺杂Fe、Cu、Ni会导致催化剂在较短时间内因硫中毒失活,尤其是Fe-Mn/TiO₂催化剂的活性中心受SO₂硫酸盐化影响最大,但是水洗再生之后其活性基本恢复,且Fe-Mn/TiO₂和Ni-Mn/TiO₂催化剂的抗硫中毒性能在水洗后得到提高。     

工业窑炉烟气氧含量对钒钛系催化剂NH3-SCR脱硝反应的影响

目前,工业窑炉主要采用钒钛系SCR催化剂对烟气中氮氧化物（NO _x ）进行控制,然而工业窑炉部分工序烟气O₂含量高,且高O₂含量对SCR反应过程的机理影响尚不明确。因此,实验研究了烟气中不同O₂含量下钒钛催化剂的脱硝活性,并采用多种表征方法系统分析了O₂含量对催化剂物理化学结构的影响;同时结合原位红外技术,进一步揭示了不同O₂含量下钒钛催化剂SCR脱硝反应机理。研究表明：在150~400℃的反应温度下,较高O₂含量可一定程度提高催化剂的低温脱硝效率,钒负载量增加可使催化剂脱硝活性温度窗口扩展且向低温区移动;催化剂在不同O₂含量条件下经过NH₃-SCR脱硝反应后,其物理结构变化不明显,反应过程中较高的O₂含量可促进催化剂表面酸循环和氧化还原循环,加速SCR脱硝反应;较高O₂含量使得SCR反应过程活性中间体 NH₃（L）和\mathrm{N}{\mathrm{H}}_{\mathrm{4}}^{+}（B）消耗加快,促进桥型硝酸盐物种的形成,从而提高其SCR脱硝活性。     

Regeneration of sulfur-poisoned CeO2 catalyst for NH3-SCR of NOx

The effects of regeneration on the activities and structure of CeO₂ catalysts for NH₃-SCR of NO_x have been studied in this article. CeO₂ catalyst is deactivated by SO₂ for NH₃-SCR of NO_x in a 200 h long-term operation at 350 °C due to the formation of sulfates, and its NO_x conversion decreases from 100% to 83% gradually. However, sulfates can be removed from sulfur-poisoned CeO₂ catalysts under high temperature thermal treatment in air. After regeneration, NO_x conversion of sulfur-poisoned CeO₂ catalyst is recovered to about 100% at 350 °C. Moreover, the regeneration temperature is related to the nature of the sulfates formed on the sulfur-poisoned CeO₂ catalysts.     

Redistributing Cu species in Cu-SSZ-13 zeolite as NH3-SCR catalyst via a simple ion-exchange

The nature and distribution of Cu species in Cu-SSZ-13 play a vital role in selective catalytic reduction of NO by NH3 (NH3-SCR),but existing methods for adjusting the Cu distribution are complex and difficult to control.Herein,we report a simple and effective ion-exchange approach to regulate the Cu distribution in the one-pot synthesized Cu-SSZ-13 that possesses sufficient initial Cu species and thus provides a "nat-ural environment" for adjusting Cu distribution precisely.By using this proposed strategy,a series of Cu-SSZ-13x zeolites with different Cu contents and distributions were obtained.It is shown that the dealu-mination of the as-synthesized Cu-SSZ-13 during the ion-exchange generates abundant vacant sites in the double six-membered-rings of the SSZ-13 zeolite for relocating Cu2+ species and thus allows the redistribution of the Cu species.The catalytic results showed that the ion-exchanged Cu-SSZ-13 zeolites exhibit quite different catalytic performance in NH3-SCR reaction but superior to the parent counterpart.The structure-activity relationship analysis indicates that the redistribution of Cu species rather than other factors (e.g.,crystallinity,chemical composition,and porous structure) is responsible for the improved NH3-SCR performance and SO2 and H2O resistance.Our work offers an effective method to pre-cisely adjust the Cu distribution in preparing the industrial SCR catalysts.     

工业窑炉烟气氧含量对钒钛系催化剂NH3-SCR脱硝反应的影响

目前,工业窑炉主要采用钒钛系SCR催化剂对烟气中氮氧化物（NO _x ）进行控制,然而工业窑炉部分工序烟气O₂含量高,且高O₂含量对SCR反应过程的机理影响尚不明确。因此,实验研究了烟气中不同O₂含量下钒钛催化剂的脱硝活性,并采用多种表征方法系统分析了O₂含量对催化剂物理化学结构的影响;同时结合原位红外技术,进一步揭示了不同O₂含量下钒钛催化剂SCR脱硝反应机理。研究表明：在150~400℃的反应温度下,较高O₂含量可一定程度提高催化剂的低温脱硝效率,钒负载量增加可使催化剂脱硝活性温度窗口扩展且向低温区移动;催化剂在不同O₂含量条件下经过NH₃-SCR脱硝反应后,其物理结构变化不明显,反应过程中较高的O₂含量可促进催化剂表面酸循环和氧化还原循环,加速SCR脱硝反应;较高O₂含量使得SCR反应过程活性中间体 NH₃（L）和\mathrm{N}{\mathrm{H}}_{\mathrm{4}}^{+}（B）消耗加快,促进桥型硝酸盐物种的形成,从而提高其SCR脱硝活性。     

An environmentally friendly FeTiSOx catalyst with a broad operation-temperature window for the NH3-SCR of NOx

A novel FeTiSO_x catalyst prepared by a simple hydrolysis coprecipitation method was used for the selective catalytic reduction (SCR) of NO_x with NH₃, which exhibited high catalytic activity (NO_x conversion of >97% and N₂ selectivity of >95%) and tolerance for both H₂O and SO₂ at a broad temperature window of ~325–475°C. The characterization results showed that the formation of Fe–O–Ti and Fe–O–S species could significantly enhance the acidic sites of the catalyst, which play an important role in NH₃ absorption and their catalytic activity. The Fe³⁺ ions in the bulk anatase TiO₂ could significantly enhance the redox properties for the SCR reaction and suppress the side reaction of NH₃ oxidation to NO or N₂O. In addition, the reaction mechanism was discussed based on in situ diffuse reflectance infrared Fourier transform spectroscopy measurements and kinetic investigation, indicating that the reaction was dominated by the Eley–Rideal mechanism over the FeTiSO_x catalyst.     

Promotion effect and mechanism of MnOx doped CeO2 nano-catalyst for NH3-SCR

MnO_x-CeO₂ (denoted as Mn–Ce) nanorod and MnO_x-CeO₂ nanooctahedra catalysts were synthesized by the hydrothermal method and were used for selective catalytic reduction of NO with NH₃. The catalytic performance tests showed that the NO removal efficiency of CeO₂ catalysts was obviously improved after loading MnO_x. The structure and properties of catalysts had been characterized by SEM、TEM、XRD、BET、XPS、H₂-TPR、NH₃-TPD and in situ DRIFTS. It was found that Mn–Ce catalyst were of uniform core-shell structure, higher concentrations of Mn⁴⁺ and Ce³⁺, better reducibility, the increase of weak acid sites. The results of in situ DRIFTS indicated that the NH₃-SCR reaction should obey the E–R mechanism. Moreover, the promotion effect and mechanism of MnO_x doped CeO₂ was demonstrated, which improved the catalytic activity of Mn–Ce catalysts.     

Vanadium Substitution as an Effective Way to Enhance the Redox Ability of Tungstophosphoric Acid and for Application of NH3-SCR

Catalysis Letters - A novel TiO2-supported vanadium-substituted tungstophosphoric acid (PW11V/TiO2) catalyst was designed and applied for selective catalytic reduction of NOx by NH3. Compared with...     

过渡金属型锰基低温NH3-SCR脱硝催化剂研究综述

综述了一元至多元过渡金属与锰的复合氧化物和负载型过渡金属与锰基催化剂的低温脱硝性能,着重阐述了在不同活性组分下,制备出不同结构的过渡金属催化剂对脱硝活性的影响。分析总结了过渡金属催化剂在低温NH₃-SCR中的反应机理及其抗水抗硫性能,最后,针对过渡金属催化剂存在的问题,展望了该领域未来可能的发展方向和研究热点。     

Study of Cu/Mn Catalysts for Coreactions of NH3-SCR and CO Oxidation

Catalysis Letters - To explore the possibility of coreaction of selective catalytic reduction with NH3 (NH3-SCR) and CO oxidation (CO-O), bimetallic doping catalysts of Mn and Cu were synthesized...     

Infrared Spectroscopic Study of the NH3-SCR on Fe-Zeolites under Transient Conditions

The standard NH₃-SCR (selective catalytic reduction) of NO/O₂-mixtures on Fe-zeolites shows significant maxima in the NO-conversion as transient response, when NH₃ is turned on and off. Introducing in situ DRIFT-spectroscopy of the catalyst two remarkable effects were observed. On the one hand a kink in the kinetics of the bands assigned to the 2H- and 3H-structure of adsorbed NH₃ was detected. Furthermore the kinetics of several bands show a maximum, which gives hint to the existence of an intermediate, in the following called SCR-SI (SCR-Surface Intermediate). Due to the observed correlation between both, the maximum in the NO-conversion and the maxima in the band kinetics on the catalyst, the SCR-SI plays an important role in the mechanism and seems to be responsible for the increased NO-conversion. In order to gain more information about the structure and role of SCR-SI the influence of temperature, iron content, O₂ concentration and NO/NH₃–ratio was studied.