低温催化脱硝技术的研究进展

面对日益严重的环境问题,燃煤烟气催化脱硝技术得到了较快发展。针对目前应用较为广泛的选择性催化还原脱硝技术,本文从催化脱硝技术的机理出发综述了低温催化脱硝方面的研究进展,将低温催化脱硝技术分成两大类:低温氨法选择性催化还原脱硝技术和低温非氨法催化脱硝技术。在低温氨法选择性催化还原脱硝技中总结了金属氧化物催化剂、分子筛催化剂以及碳基催化剂等的反应机理和反应过程,揭示了影响脱硝效率的各种因素;低温非氨法催化脱硝技术中从反应方式出发,总结了NO_x催化裂解技术、HC-SCR技术、NO_x吸附-还原技术以及CO催化脱硝技术的研究进展,并对反应影响因素进行了综述。探索了各种催化剂的优势和不足之处:低温NH₃-SCR技术具有选择性高、效率高的特点但是其还原剂价格较贵且存储运输较为困难;低温非氨法催化脱硝技术选择性差、效率低,但是还原剂价格低廉、易于制备,且在工艺方面改进时可以达到要求的效率。在此基础上本文展望了未来低温催化脱硝的研究方向:在降低脱硝成本的情况下改善催化脱硝工艺,大力发展氮氧化物吸附还原等技术。     

Catalytic reduction system of NOx in exhaust gases from diesel engines with secondary fuel injection

Catalytic NO_x reduction system with secondary fuel injection was studied not only in a laboratory scale, but also in a large bench scale. Diesel fuel was injected before the catalyst bed, and the activity and durability of the catalyst for the NO_x reduction were tested. Using the fuel as a reductant, silver aluminate supported on alumina was selected as the most active and suitable catalyst. The resistance of the silver aluminate catalyst to SO_x was enhanced by the addition of a small amount of WO₃, MoO₃ and Pt. It was found from the engine bench test that NO_x conversion increased in proportion to the amount of aldehydes formed from the injected fuel in the exhaust gas. Thus, the secondary fuel injection into exhaust gas through a partial oxidation catalyst enhanced the NO_x conversion. At 450°C, the engine bench test exhibited maximum NO_x conversion of 75% and 45% at the SV of 15 000 and 70 000 h⁻¹, respectively.     

Circumventing fuel-NOx formation in catalytic combustion of gasified biomass

It has been shown that it is possible to decrease fuel-NO_x produced from NH₃ using catalytic combustion of a synthetic gasified biomass at fuel-lean conditions. In a certain temperature regime where the conversion of fuel components, such as CO, H₂ and CH₄, is low and conversion of NH₃ is high, it is suggested that the formed NO_x is reduced by the remaining fuel components, mainly hydrocarbons. With oxide catalysts only ca. 10% of the NH₃ was converted to NO_x, the rest to N₂. It has also been shown that the ignition sequence of CO, H₂ and CH₄ varied for different catalysts and different experimental conditions, and that methane coupling and methanation reactions occurred before ignition of CH₄.     

Development of a catalytically assisted combustor for a gas turbine

A catalytically assisted low NO_x combustor has been developed which has the advantage of catalyst durability. This combustor is composed of a burner section and a premixed combustion section behind the burner section. The burner system consists of six catalytic combustor segments and six premixing nozzles, which are arranged alternately and in parallel. Fuel flow rate for the catalysts and the premixing nozzles are controlled independently. The catalytic combustion temperature is maintained under 1000°C, additional premixed gas is injected from the premixing nozzles into the catalytic combustion gas, and lean premixed combustion at 1300°C is carried out in the premixed combustion section. This system was designed to avoid catalytic deactivation at high temperature and thermal or mechanical shock fracture of the honeycomb monolith. In order to maintain the catalyst temperature under 1000°C, the combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected for the combustor test. A combustor for a 20 MW class multi-can type gas turbine was designed and tested under high pressure conditions using LNG fuel. Measurements of NO_x, CO and unburned hydrocarbon were made and other measurements were made to evaluate combustor performance under various combustion temperatures and pressures. As a result of the tests, it was proved that NO_x emission was lower than 10 ppm converted at 16% O₂, combustion efficiency was almost 100% at 1300°C of combustor outlet temperature and 13.5 ata of combustor inlet pressure.     

脱硝协同汞氧化聚苯硫醚四元催化滤料制备方法及理化特性

采用原位氧化法（ISM）、浸渍煅烧法（ICM）和涂覆法（CM）制备聚苯硫醚（PPS）双效催化滤料,在模拟烟气固定床系统中考察了滤料低温NO_x催化协同Hg⁰氧化性能,深入分析了原位氧化滤料表面形貌、元素分布、晶态结构和Hg及NO_x赋存形态。结果表明：在相同条件下,3种制备方法对应滤料催化活性大小顺序为Mn-Ce-Fe-Co-O_x/PPS@ISM＞Mn-Ce-Fe-Co-O_x/PPS@ICM＞Mn-Ce-Fe-Co-O_x/PPS@CM。ISM对应PPS单层饱和负载量约为0.9,活性反应温度窗口为110~210℃,其中170℃时Mn-Ce-Fe-Co-O_x/PPS@ISM的非均相NO氧化、NO_x还原和Hg⁰氧化效率最高分别达到8.6%、84.6%和93.2%。程序升温脱附实验结果表明：(0.9)Mn-Ce-Fe-Co-O_x/PPS@ ISM表面NO_x吸附活性位点中弱碱位数量占优,而中碱位化学吸附NO主要以NO_y（y=2或3）结构存在,歧化态NO₂次之。同时,Hg与NO在氧气条件下以非均相反应途径转化为HgO和Hg(NO₃)₂/Hg₂(NO₃)₂。表征结果表明：ISM制备的MnO_x、CeO_x、CoO_x和Fe₂O₃复合氧化物呈弱晶相、高度分散团絮状结构赋存于PPS@ISM纤维。     

Selective catalytic reduction of NO by C3H8 over CoOx/Al2O3: An investigation of structure–activity relationships

A series of CoO_x/Al₂O₃ catalysts was prepared, characterized, and applied for the selective catalytic reduction (SCR) of NO by C₃H₈. The results of XRD, UV–vis, IR, Far-IR and ESR characterizations of the catalysts suggest that the predominant oxidation state of cobalt species is +2 for the catalysts with low cobalt loading (≤2 mol%) and for the catalysts with 4 mol% cobalt loading prepared by sol–gel and co-precipitation. Co₃O₄ crystallites or agglomerates are the predominant species in the catalysts with high cobalt loading prepared by incipient wetness impregnation and solid dispersion. An optimized CoO_x/Al₂O₃ catalyst shows high activity in SCR of NO by C₃H₈ (100% conversion of NO at 723 K, GHSV: 10,000 h⁻¹). The activity of the selective catalytic reduction of NO by C₃H₈ increases with the increase of cobalt–alumina interactions in the catalysts. The influences of cobalt loading and catalyst preparation method on the catalytic performance suggest that tiny CoAl₂O₄ crystallites highly dispersed on alumina are responsible for the efficient catalytic reduction of NO, whereas Co₃O₄ crystallites catalyze the combustion of C₃H₈ only.     

负载型Mn基低温NH3-SCR脱硝催化剂研究综述

MnO_x以其良好的低温催化活性成为当前低温NH₃-SCR脱硝催化剂研究的热点,负载型Mn基低温脱硝催化剂较好地解决了非负载型低温N₂选择性差、易中毒等难题,具有良好的工业应用前景.本文综述了负载型Mn基低温脱硝催化剂的研究现状,从活性组分、载体、制备方法、机理和动力学以及抗H₂O、SO₂性能5个方面介绍了负载型Mn基低温脱硝催化剂的研究现状,着重阐述了金属氧化物、分子筛、炭基等人工和天然载体负载MnO_x在制备方法和脱硝活性方面的最新研究成果,简述了Mn基低温脱硝催化剂的催化机理以及动力学研究进展,分析了Mn基低温脱硝催化剂的H₂O和SO₂中毒机理.指出提高负载型Mn基低温脱硝催化剂的抗中毒性能和再生是今后研究的重点.     

NOx removal from the flue gas of oil-fired boiler using a multistage plasma-catalyst hybrid system

The study on removal of NO_x from the flue gas of oil-fired boiler has been carried out using non-thermal plasma cum catalyst hybrid reactor at 150 °C. Propylene (C₃H₆) was used as a reducing agent. A multistage plasma-catalyst hybrid reactor was newly designed and successfully operated to clean up the flue gas stream having a flow rate of 30 Nm³/h. TiO₂ and Pd/ZrO₂ wash-coated on cordierite honeycomb were used as catalysts in the present study. Though the plasma-catalyst hybrid reactor with TiO₂ showed good activity on the removal of NO yet it removed only 50–60% of NO_x because a significant portion of NO oxidized to NO₂. On the contrary, the plasma-catalyst hybrid reactor with Pd/ZrO₂ removed about 50% of inlet NO with a negligible amount of NO oxidation into NO₂. The plasma/dual-catalysts hybrid system (front two units of plasma-Pd/ZrO₂ + rear two units of plasma/TiO₂) proved to be very promising in NO_x removal in the presence of C₃H₆. DeNO_x efficiency of about 74% has been achieved at a space velocity of 3300/h at 150 °C.     

被动NOx吸附剂在柴油车冷启动排放控制中的研究进展

机动车尾气是氮氧化物（NO_x）重要来源之一,常见柴油车尾气NO_x处理技术对冷启动阶段NO_x减排效果较差,被动NO_x吸附剂（PNA）应运而生。PNA可低温吸附存储NO_x、高温脱附释放NO_x,释放的NO_x经过下游NO_x处理单元[选择性催化还原（SCR）或NO_x储存还原（NSR）]被彻底净化。本文综述了近年来PNA材料在低温冷启动过程中净化NO_x的研究进展,对不同类型PNA材料进行结构及性能比对,其中Pd/分子筛表现出良好的低温NO_x吸附-脱附性能、抗硫性以及水热稳定性,成为PNA优选。深入讨论了Pd/分子筛存储NO_x机制以及影响因素。此外,分析了PNA在低温吸附-脱附NO_x中面临的问题并展望其前景,指出提高具有优异抗水性能的NO_x吸附位点数量及Pd物种分散程度是开发高性能PNA的重要前提。     

Catalysis of H2, CO and alkane oxidation–combustion over Pt/Silica catalysts: evidence of coupling and promotion

Results are presented on the oxidative–combustion reactions of H₂, CO, methane and propane over polycrystalline-powdered silica-supported catalysts containing Pt (and possibly oxide promoters, e.g. MnO₂, etc.) and the coupling of different combustion processes and also heterogeneous–homogeneous reactions. The Pt/silica catalysts appear to mature with use. Catalysed combustions take place, as expected, at far lower temperatures and with smaller activation energies than the homogeneous reactions. The role of added or intermediate (i.e. produced by alkane partial oxidation or steam reforming) H₂ in accelerating and lowering the temperatures of catalysed alkane combustions and hence minimising NO_x emission is considered with regard to the dispersion of the Pt, as is bifurcative–hysteretic combustion in the catalysed reaction, prevalent for CO, but less certain for H₂ or alkanes. CO decelerates the catalysed combustion of hydrogen on supported Pt (and may also do this for alkane combustion). Whether the acceleration due to intermediate H₂ in alkane combustion exceeds the deceleration due to intermediate CO remains to be seen, but it may be that the water–gas shift reaction moves the advantage to H₂. Further study by in situ methods will be needed to optimise and understand this coupling so that it can be used to maximise efficient alkane-catalysed combustion with minimum NO_x production. This should also lead to higher turnover numbers (which are at present quite low for propane-catalysed combustion).     

Lean reduction of NO by C3H6 over Ag/alumina derived from Al2O3, AlOOH and Al(OH)3

The effectiveness of Ag/Al₂O₃ catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al₂O₃, and Al(OH)₃ was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O₂, NO + O₂-temperature programmed desorption (TPD), H₂-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C₃H₆-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C₃H₆ conversion was achieved over Ag/Al₂O₃ (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al₂O₃ (I) is deemed to be crucial for NO selective reduction into N₂. By contrast, a high C₃H₆ conversion simultaneously with a moderate N₂ yield was observed over Ag/Al₂O₃ (II) prepared from a γ-Al₂O₃ source. The larger particles of Ag_mO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al₂O₃ (III) was obtained via employing a Al(OH)₃ source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al₂O₃ (I). A subsequent calcination of Ag/Al₂O₃ (III) at 800 °C led to the generation of Ag/Al₂O₃ (IV) catalyst yielding a significant enhancement in both N₂ yield and C₃H₆ conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al₂O₃ (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al₂O₃ (II and V) > Ag/Al₂O₃ (IV) > Ag/Al₂O₃ (I) > Ag/Al₂O₃ (III) and Al₂O₃ (I). The formation of nitrate species is an important step for the deNO_x process, which can be promoted by increasing O₂ feed concentration as evidenced by NO + O₂-TPD study for Ag/Al₂O₃ (I), achieving a better catalytic performance.     

半导体材料在光催化低浓度氮氧化物的研究进展

氮氧化物（NO_x）是一类有害的空气污染物,会引发酸雨、雾霾、光化学烟雾等严重的环境问题。目前,如何有效地去除空气中低浓度的NO_x（十亿分之一）是研究的热点和难点。半导体光催化氧化法可以将空气中低浓度NO_x氧化成无毒的硝酸盐,是一种经济有效的净化技术之一。本文主要围绕二氧化钛（TiO₂）,氮化碳（g-C₃N₄）和Bi系三类半导体光催化材料,对近年来包括本课题组在内的国内外对光催化去除低浓度NO_x研究进行了简要概述。其中,通过代表性的工作介绍了贵金属沉积、元素掺杂、构建异质结和表面空位缺陷工程等改性策略,以提高半导体材料在去除低浓度NO_x的光催化活性和性能。此外,对半导体材料在光净化低浓度NO_x的未来发展进行了展望,以期待为高性能半导体光催化剂的理性设计和制备以及催化机理的探索等方面的研究提供思路。     

V2O5-MoO3/Tio2催化滤袋的制备及中试应用

为解决现有Mn基催化滤袋SO₂中毒的问题,制备了基于V₂O₅-MoO₃/TiO₂的催化滤袋,用于在180~260℃范围内同时去除NO_x和粉尘。实验结果表明,双层滤袋在气体过滤面速度为0.2 m/min时具有良好的脱硝活性和抗硫抗水性能。在纯氧玻璃窑炉中试中采用制备的双层催化滤袋进行了试验,烟气量为2000~3000 m³/h、SO₂浓度在20~30 mg/m³范围内、水蒸气含量10%（体积分数）、NO_x浓度为400~550 mg/m³,在170~210℃范围内NO_x转化率可达到88.14%~95.06%,验证了催化滤袋的脱硝性能;连续运行1500 h后,活性出现5%左右的微弱衰减;在高硫烟气条件下（300~500 mg/m³）连续运行100 h发现催化滤袋失活,SEM-EDS和XPS表征证明催化剂失活是由于硫铵类物质在滤袋纤维表面沉积,部分活性位点被覆盖所致。     

内/外烟气再循环对天然气燃烧NOx生成的影响

烟气再循环作为一种有效抑制NO_x生成的技术,广泛应用于化工、制药和酿酒等行业的天然气低氮燃烧过程,其作用机理是学术界和工业界关注的热点。本文根据内/外烟气再循环的作用不同,设计了弱/强内烟气再循环两种扩散式燃烧器,结合外烟气再循环技术,在0.8MW中试实验台上研究了内/外烟气再循环对天然气燃烧过程NO_x生成的影响规律,同时开展了Fluent数值模拟。结果表明：内烟气再循环能够有效抑制NO_x的生成,同时保证燃烧稳定。相同工况下,带内烟气再循环燃烧器初始排放远低于传统低氮燃烧器。同时结合外烟气再循环技术,可使NO_x排放量维持在30mg/m³以下。Fluent模拟结果显示了外烟气再循环能够显著地降低天然气燃烧火焰区的温度和O₂浓度。其中温度的降低对于NO_x生成的抑制起到了决定性的作用。当NO_x降低到约30mg/m³时,快速型NO_x对整体NO_x生成的贡献超过热力型NO_x,此情况下必须考虑对快速型NO_x进行抑制。     

The effect of hydrogen on the selective catalytic reduction of NO in excess oxygen over Ag/Al2O3

The selective catalytic reduction (SCR) of nitrogen oxides (NO_x) by propane in the presence of H₂ on sol–gel prepared Ag/Al₂O₃ catalysts (0.5–5 wt.% Ag) was investigated. It was confirmed that hydrocarbon-assisted SCR of NO_x is remarkably enhanced by co-feeding hydrogen to a lean exhaust gas mixture (λ>1), attaining considerable activity within a wide temperature window (470–825 K). The samples had marginal activity at 575 K without co-fed H₂, but achieved up to 60% NO_x conversion in the presence of H₂ at a space velocity of 30,000 h⁻¹. NO₂ as NO_x feed component is not converted to N₂ by C₃H₈ to a substantial extent under lean conditions. This points to an activation route of NO through direct conversion to adsorbed nitrite/nitrate or to a dissociation of NO over Ag⁰, formed through short-term reduction by H₂. The nature of Ag species was characterized by X-ray diffraction, temperature-programmed reduction, pulse thermoanalytical measurements, electron microscopy and FTIR spectroscopy. It could be shown that Ag₂O nano-sized clusters are predominantly present on all samples, whereas formation of silver aluminate could not be confirmed. Nano-sized Ag₂O clusters can reversibly be reduced/reoxidized by H₂. A silver loading higher than 2 wt.% leads to a part of Ag₂O particles, which are thermally decomposed during calcination at 800 K or higher. The catalytic role of this metallic silver is still unclear. Formal kinetic analysis of catalytic data revealed that the activation energy of the overall reaction is significantly lowered in the presence of H₂. The presence of water does not change the activation energy. It is concluded that hydrogen reduces the nano-sized Ag₂O clusters to Ag⁰ on a short-term scale. Zero-valent silver promotes a dissociation pathway of NO_x conversion. The fact that more oxidized ad-species (nitrite/nitrate) are observed in the presence of H₂ is attributed to a dissociative activation of gas-phase oxygen on Ag⁰.     

废钒钛基SCR催化剂的处置方法研究进展

当前中国燃煤发电量仍占总发电量很大比重,燃煤电厂会产生大量的氮氧化物,其会对人体和环境造成危害。因此,处理好燃煤电厂产生的氮氧化物十分重要。选择性催化还原（SCR）技术是控制氮氧化物排放的重要手段。而作为该技术的核心,大量的钒钛基SCR催化剂被应用到燃煤电厂氮氧化物的处理工艺中,对废弃的SCR催化剂进行妥善处理也成为了急需解决的问题。本文对相应背景下的文献进行了系统整理,介绍了催化剂再生处理工艺以及有价金属回收技术的最新研究,分析了与再生处理工艺以及有价金属回收技术优化相关的挑战,提出了有关如何开发高效催化剂再生处理工艺以及有价金属回收技术的建议,以推动该方向的进一步研究。     

Ce-MnOx低温净化氮氧化物和一氧化碳的催化性能研究

为协助工业界实现碳达峰与碳中和的目标,聚焦于低温烟气中氮氧化物（NO_x）和一氧化碳（CO）的协同脱除,以铈（Ce）和锰（Mn）的无机盐为前驱体,采用共沉淀法、机械球磨法、溶液燃烧法和溶胶-凝胶法制备了Ce元素改性的Mn基氨选择性催化还原（NH₃-SCR）/一氧化碳（CO）氧化双效纳米催化剂。使用固定床-在线质谱/色谱测试系统对催化剂性能进行了评价,并利用X射线衍射、氮气-物理吸附等表征手段对Ce-MnO_x纳米催化剂进行了表征分析。结果表明,反向共沉淀法制备的催化剂具有最优的NO_x和CO协同脱除性能,在100 000 mL/（g·h）的高空速条件下,140 ℃以上能够实现CO净化率超过85%,100 ℃以上能够脱除气体中80%以上的NO_x,且运行20 h后仅出现微弱的性能衰减。其活性组分为具有高比表面积（100 m²/g以上）的CeMnO_x,因此能够吸附更多气体进行反应,表现出优异的催化性能。     

水泥窑协同处置垃圾衍生燃料对NOx和SO2生成转化的影响

利用水泥窑协同处置垃圾衍生燃料是目前发展趋势之一,但实际处置过程中存在着污染物排放不稳定的问题,因此本文以湖北某水泥厂处置的垃圾衍生燃料为研究对象,利用高温管式炉开展试验,研究了五种垃圾衍生燃料在500～900℃的燃烧环境下燃烧产物NOx、SO2的释放特点.试验结果表明:垃圾衍生燃料在不同温度下燃烧过程中NOx的浓度峰...     

Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Deactivation by SO2 of MnOx/Al2O3 catalysts used for the selective catalytic reduction of NO with NH3 at low temperatures

Low loaded alumina supported manganese oxides exhibit a high activity and selectivity for the selective catalytic reduction (SCR) of NO in the temperature range 383–623 K. The impact of low concentrations of SO₂ on the activity of these catalysts has been investigated. Upon SO₂ addition to the flue gas, the catalysts lose their high initial activity in a few hours due to stoichiometric SO₂ uptake. Analysis of the deactivated samples by mercury porosimetry, FTIR, TPR and TPD shows that the deactivation is not due to the formation of (bulk or surface) Al₂(SO₄)₃ or deposition of ammonium sulphates. Comparison of the results with unsupported Mn₂O₃ and MnO₂ provides evidence that formation of surface MnSO₄ is the main deactivation route. This process is independent of the oxidation state of the manganese and the presence of oxygen in the gas stream. The formed sulphates decompose at 1020 K and are reduced by H₂ at temperatures above 810 K. This means that regeneration of the catalysts is not very feasible. The results restrict practical application of these catalysts to sulphur free conditions.