V2O5/TiO2催化剂中毒机理的试验研究

选择性催化还原(SCR)催化剂是SCR烟气脱硝技术的核心,是整个SCR系统脱硝效率和经济性的决定因素.本文工作的主要研究思路是以钒钛SCR催化剂为研究对象,研究了H2O和SO2,以及相同含量下K、Na、Ca、Pb的氧化物对钒钛催化剂NO转化率的影响.H2O的存在会抑制V2O5/TiO2催化剂脱硝活性,而SO2在一定程度上促进(V2O5/TiO2)催化剂的SCR脱硝反应,提高NO转化率;碱金属K对钒钛催化剂的钝化作用都是最强,K2O和Na2O的掺入会抑制钒钛催化剂上V2O5的还原能力,而CaO和PbO的掺入对钒钛催化剂上V2O5的还原能力影响较小.     

Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3

Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction （SCR） of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.     

富氧条件下SnO2/Al2O3催化剂上丙烯选择性还原NOx的研究

考察了分别用浸渍法、共沉淀法和溶胶-凝胶法制备的SnO₂/Al₂O₃催化剂上丙烯选择性还原NO_x的催化活性,发现制备方法与Sn的负载量对其活性有重要影响.溶胶-凝胶法制备的SnO₂/Al₂O₃催化剂活性最高,Sn的最佳负载量为5%.与浸渍法和共沉淀法制备的5%SnO₂/Al₂O₃催化剂相比,溶胶-凝胶法制备的5%SnO₂/Al₂O₃催化剂受水蒸汽的抑制作用较弱,并且在水和SO₂共存的条件下活性最高.此外,反应气中丙烯及氧气浓度的增加有利于NO_x转化率的提高.     

Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst

CeO2–TiO2composite supports with different Ce/Ti molar ratios were prepared by a homogeneous precipitation method, and V2O5–WO3/CeO2–TiO2catalysts for the selective catalytic reduction（SCR） of NOx with NH3 were prepared by an incipient-wetness impregnation method. These catalysts were characterized by means of BET, XRD, UV–Vis,Raman and XPS techniques. The results showed that the catalytic activity of V2O5–WO3/TiO2 was greatly enhanced by Ce doping（molar ratio of Ce/Ti = 1/10） in the TiO2 support.The catalysts that were predominantly anatase TiO2 showed better catalytic performance than the catalysts that were predominantly fluorite CeO2. The Ce additive could enhance the surface adsorbed oxygen and accelerate the SCR reaction. The effects of O2 concentration, ratio of NH3/NO, space velocity and SO2 on the catalytic activity were also investigated. The presence of oxygen played an important role in NO reduction. The optimal ratio of NH3/NO was 1/1 and the catalyst had good resistance to SO2 poisoning.     

Effect of MoO3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Pt/CeO2催化氧化甲苯反应机制研究

采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.     

不同方法制备Co3O4催化剂CO-SCR性能及机制

氮氧化物(NOx)是造成细颗粒物、近地面臭氧等大气污染问题的重要前体物.随着大气污染治理行动的深入,对工业锅炉/窑炉烟气排放的NOx进行控制十分重要.采用不同方法制备了一系列Co_3O_4催化剂,考察了不同制备方法对CO选择性催化还原NO(CO-SCR)反应活性的影响,通过BET、XRD、Raman、HR-TEM和SEM等技术对该系列催化剂进行了表征.活性测试表明,以硫酸钴为前驱体用固态研磨法制备的Co_3O_4-S催化剂具有更优异的CO-SCR反应活性,且表现出较好的抗水蒸气性能,以醋酸钴为前驱体用固态研磨法制备的Co_3O_4-C催化剂显示出较好的抗水性能. NO氧化结果显示,催化剂的NO氧化效果越好,CO-SCR活性也越好. Raman表征结果显示,Co_3O_4-S表面可能含有更多的Co2+离子,从而有利于形成氧空位. H2-TPR结果表明,Co_3O_4-S催化剂的氧化还原性较好. HR-TEM表征发现Co_3O_4-S和Co_3O_4-O主要暴露(111)和(220)晶面,而更多(220)晶面的暴露可能更有利于反应的进行.     

Catalytic oxidation of benzene over nanostructured porous Co3O4-CeO2 composite catalysts

The three-dimensional structured Co₃O₄-CeO₂ oxides with Co/Ce molar ratio 16:1 gave the highest catalytic activity, which provided more surface hydroxyl groups and more surface oxygenated species.     

Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.     

A comparative study of Mn/CeO2, Mn/ZrO2 and Mn/Ce-ZrO2 for low temperature selective catalytic reduction of NO with NH3 in the presence of SO2 and H2O

Ce-ZrO2 is a widely used three-way catalyst support.Because of the large surface area and excellent redox quality,Ce-ZrO2 may have potential application in selective catalytic reduction(SCR) systems.In the present work,Ce-ZrO2 was introduced into a low-temperature SCR system and CeO2 and ZrO2 supports were also introduced to make a contrastive study.Mn/CeO2,Mn/ZrO2 and Mn/Ce-ZrO2 were prepared by impregnating these supports with Mn(NO3)2 solution,and have been characterized by N2-BET,XRD,TPR,TPD,XPS,FT-IR and TG.The activity and resistance to SO2 and H2O of the catalysts were investigated.Mn/Ce-ZrO2 and Mn/CeO2 were proved to have better low-temperature activities than Mn/ZrO2,and yielded 98.6% and 96.8% NO conversion at 180°C,respectively.This is mainly because Mn/Ce-ZrO2 and Mn/CeO2 had higher dispersion of manganese oxides,better redox properties and more weakly adsorbed oxygen species than Mn/ZrO2.In addition,Mn/Ce-ZrO2 showed a good resistance to SO2 and H2O and presented 87.1% NO conversion,even under SO2 and H2O treatment for 6 hours,and the activity of Mn/Ce-ZrO2 was almost restored to its original level after cutting off the injection of SO2 and H2O.This was due to the weak water absorption and weak sulfation process on the surface of the catalyst.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

CeO2改性MnOx/Al2O3的低温SCR法脱硝性能及机制研究

采用凝胶溶胶法制备大比表面积的Al2O3载体,等体积浸渍法配制负载MnOx和CeO2组分的CeO2-MnOx催化剂.以NH3为还原剂,一定的空气流速及合适的气体配比的条件下,考察所制备的催化剂在70～300℃范围内低温SCR法的脱硝性能及机制,同时分别对催化剂进行BET、XRD、SEM等表征实验,研究催化剂的理化性质....     

Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

The effect of pretreatment on Pd/Al₂O₃ catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al₂O₃ catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al₂O₃ activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al₂O₃ pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al₂O₃, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al₂O₃ catalyst for the catalytic oxidation of o-xylene at low temperature.     

Fe2O3添加对钛基SCR催化剂表面硫酸氢铵分解行为的影响规律

采用共沉淀法合成了TiO_2及TiO_2-Fe_2O_3载体,并对硫酸氢铵与上述载体之间的相互作用及硫酸氢铵的具体分解行为进行了研究.结果表明,催化剂载体表面含硫官能团主要以双齿硫酸盐的形式存在,含氮官能团以铵根离子的形式存在.当硫酸氢铵沉积于催化剂载体表面时,由于硫酸根离子具有较强的电负性,Ti原子及Fe原子处于电子缺失状态.对于TiO_2载体,硫酸根离子主要与Ti原子相连;而对于TiO_2-Fe_2O_3载体,Ti原子及Fe原子均为硫酸根离子主要的附着位点.采用热分析方法及原位红外对硫酸氢铵在TiO_2及TiO_2-Fe_2O_3载体表面的分解行为进行了研究,发现铁氧化物的添加显著促进了硫酸氢铵在低温区间内的分解行为;与铵根离子相比,硫酸根离子具有更高的热稳定性.催化剂稳定性测试结果表明,铁氧化物的添加显著提高了低温抗硫抗水性能,为实现低温SCR技术的工业应用提供了理论基础.     

O3/H2O2氧化苯乙烯气体性能及机制

O3/H2O2体系能产生大量自由基,臭氧与自由基的耦合氧化作用能提高苯乙烯的氧化去除效率.采用O3/H2O2氧化高浓度苯乙烯有机废气,研究了臭氧投加量、停留时间、H2O2体积分数、循环液喷淋密度和O3/C8H8摩尔比对苯乙烯去除率的影响.结果表明,O3/H2O2气液两相氧化能高效净化苯乙烯有机废气,苯乙烯去除率可达85.7%.适宜运行条件:停留时间为20.6 s,H2O2体积分数为10%,喷淋密度为1.72 m3·(m2·h)-1,O3/C8H8摩尔比为0.46.采用GC-MS分析O3/H2O2气液两相高级氧化苯乙烯出口气样,研究结果表明苯甲醛(C6H5CHO)和苯甲酸(C6H5COOH)为O3/H2O2氧化苯乙烯的中间产物,并推测出苯乙烯的降解机制.     

钒和钨负载量对V2O5-WO3/TiO2表面形态及催化性能的影响

采用浸渍法制备了一系列不同钒和钨负载量的V₂O₅-WO₃/TiO₂催化剂样品,对样品NH₃选择性催化还原NO性能进行了评价,并用BET、XRD、XPS等手段对催化剂样品的表面形态进行了表征.研究发现,钒的负载量对催化剂的比表面积和催化活性有显著影响,当钒负载量从1％升高到8％时,催化剂比表面积下降了16 m²/g,最高活性温度降低了约100℃.钨起到稳定剂和助剂的双重作用,当钒负载量为1％时,钨负载量从0升高到6％,催化剂比表面积仅下降了3 m²/g,而活性温度窗口向高温和低温各拓宽了约50℃.研究表明钒和钨负载量都能影响催化剂表面的VO_x物种,但对催化剂的表面晶型没有明显影响.     

SO2对MnOx/PG催化剂低温脱硝的影响机理研究

采用等体积浸渍法制备了锰氧化物负载凹凸棒石(MnO_x/PG)低温SCR催化剂,通过SO₂暂态响应、程序升温表面反应(TPSR)等实验技术研究了烟气中SO₂对催化剂SCR脱硝活性的影响行为.采用程序升温脱附(TPD)、BET比表面及孔径分布测定、XPS等表征技术对催化剂硫中毒的机理及化学本质进行了深入分析.结果表明,低温下烟气中SO₂对MnO_x/PG催化剂的SCR脱硝活性存在显著的抑制作用,催化剂中毒主要由烟气中SO₂的催化氧化引起.一方面SO₂氧化为SO₃后与NH₃及H₂O竞争反应形成复杂的硫酸铵盐堵塞催化剂孔道,另一方面与活性组分MnO₂结合形成MnSO₄使得部分活性组分形态发生变迁.其中硫酸铵盐的形成可通过适当的热处理得以去除,而MnSO₄则不可恢复,但催化剂SCR活性却显著增加,表明MnSO₄的形成不是催化剂失活的主要因素.吸附态的硫可显著增加催化剂表面酸性,因此对SCR活性有促进作用.催化剂失活主要机理为:由气相SO₂的连续氧化并与NH₃相结合形成硫酸铵盐,并且在低温下难以分解,以致堵塞催化剂活性中心.     

Effects of synthesis methods on catalytic activities of CoOx–TiO2 for low-temperature NH3-SCR of NO

A series of cobalt doped TiO_2(Co-TiO_2) and Co Oxloaded TiO_2(Co/TiO_2) catalysts prepared by sol–gel and impregnation methods respectively were investigated on selective catalytic reduction with NH_3(NH_3-SCR) of NO. It was found that Co-TiO_2 catalyst showed more preferable catalytic activity at low temperature range. From characterization results of XRD,TEM, Raman and FT-IR, Co species were proved to be doped into TiO_2 lattice by replaced Ti atoms. After being characterized and analyzed by NH_3-TPD, PL, XPS, EPR and DRIFTS, it was found that the better NH_3-SCR activities of Co-TiO_2 catalysts, compared with Co/TiO_2 catalyst, were ascribed to the formation of more oxygen vacancies which further promoted the production of more superoxide ions(O-2). The superoxide ions were crucial for the formation of low temperature SCR reaction intermediates(NO-3) by reacting with adsorbed NO molecule. Therefore, these aspects were responsible for the higher low temperature NH_3-SCR activity of Co-TiO_2 catalysts.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.