NH3-SCR performance and the resistance to SO2 for Nb doped vanadium based catalyst at low temperatures

Niobium oxide as the promoter was doped in the V/WTi catalyst for the selective catalytic reduction(SCR)of NO.The results showed that the addition of Nb_2O_5could improve the SCR activity at low temperatures and the 6 wt.%additive was an appropriate dosage.The enhanced reaction activity of adsorbed ammonia species and the improved dispersion of vanadium oxide might be the reasons for the elevation of SCR activity at low temperatures.The resistances to SO_2of 3V6Nb/WTi catalyst at different temperatures were investigated.FTIR spectrum and TG-FTIR result indicated that the deposition of ammonium sulfate species was the main deactivation reason at low temperatures,which still exhibited the reactivity with NO above 200°C on the catalyst surface.There was a synergistic effect among NH_3,H_2O and SO_2that NH_3and H_2O both accelerated the catalyst deactivation in the presence of SO_2at 175°C.The thermal treatment at 400°C could regenerate the deactivated catalyst and get SCR activity recovered.The particle and monolith catalysts both kept stable NO_xconversion at 225°C with high concentration of H_2O and SO_2during the long time tests.     

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.     

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.     

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.     

低温条件下Nano-MnOx上NH3选择性催化还原NO

采用流变相法制备了无载体Nano-MnO_x催化剂,在低温条件下(50～150℃)以NH₃为还原剂系统考察了氮氧化物的选择催化还原特性.结果表明,流变相法制备的Nano-MnO_x催化剂具有良好的低温催化活性.实验条件下,80℃即可获得98.25%的NO转化率,100～150℃内NO几乎完全转化;SO₂和H₂Ｏ会与NO和NH₃在催化剂表面产生竞争吸附,导致催化活性下降,但该影响是可逆的.经分析,较大的比表面积和较低的晶化度是Nano-MnO_x具有良好低温活性的2个主要原因.     

Mn-Ce-Co/TiO2催化剂低温脱硝活性研究

以纳米TiO2为载体,通过浸渍法制备一系列改性Mn-Ce/TiO2脱硝催化剂.通过实验考察不同元素组分催化剂的脱硝活性,同时探讨金属氧化物掺杂对提高催化剂低温脱硝活性的机理.活性测试结果显示,Co掺杂能最有效地提高Mn-Ce/TiO2催化剂在低温段的SCR脱硝活性,在n(Co):n(TiO2)=0.08～0.10、体积空速为35100h-1的条件下,催化剂在120℃时就能达到80%以上的NO去除率,140℃左右时的NO去除率接近100%.BET、XRD、TPR、TPD等表征测试结果表明,Co掺杂可改进Mn-Ce/TiO2催化剂的物化特性,增加催化剂表面的活性酸位点及活性氧数量,提高催化剂的氧化还原能力,从而提高Mn-Ce/TiO2催化剂低温SCR脱硝活性.     

Na2SO4中毒SCR催化剂对SO3生成特性的影响

为研究Na₂SO₄中毒SCR催化剂（V₂O₅-WO₃/TiO₂催化剂）对SO₃生成特性的影响,采用湿式浸渍法制备w（Na）为3%的Na₂SO₄中毒SCR催化剂,并通过N₂物理吸附/脱附、XRD（X射线衍射）技术、SEM（扫描电镜）、XPS（X射线光电子能谱）分析技术对催化剂的物理化学特性进行表征.结果表明:①随着反应温度的升高,所有催化剂上的SO₃生成率逐渐增加.当温度升至490℃时,SCR催化剂上的SO₃生成率为0.85%,而3% Na₂SO₄中毒SCR催化剂上的SO₃生成率高达1.36%.SO₄2-的存在导致V-O-S增多,从而促进SO₃的生成.②随入口ρ（SO₂）的增加,SO₃生成率呈下降的趋势.当入口ρ（SO₂）为1 000 mg/m3时,3% Na₂SO₄中毒SCR催化剂上的SO₃生成率为1.02%,而SCR催化剂上仅为0.60%.ρ（SO₂）对SO₃生成率的影响主要依赖于温度和催化剂活性位点数等.③N₂物理吸附/脱附、XRD和SEM表征结果表明,与SCR催化剂相比,Na₂SO₄中毒SCR催化剂表面有Na₂SO₄的积聚,出现了裂纹和大孔隙,催化剂的比表面积和孔容下降,这些变化均不利于催化剂的催化性能;XPS结果表明,Na₂SO₄的加入提高了表面化学吸附氧含量,降低了活性组分中w（V4+）/w（V5+）的值.研究显示,相比于SCR催化剂,Na₂SO₄中毒SCR催化剂上的SO₃生成率大幅增加.      

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.     

SO2对CoH-ZSM-5催化CH4还原NO催化性能的影响

研究了富氧条件下SO₂对CoH-ZSM-5上CH₄选择还原NO(CH₄-SCR)的影响,应用SO₂-TPSR,NO+(O₂)-TPD等方法研究了产生中毒的原因并定量研究了被毒化的活性位.反应在773 K进行时,加入体积分数78×10^-6SO₂,NO的转化率由72%逐渐降低并稳定在58%,提高反应温度至823 K,NO稳定转化率上升至62%.同时加入2.5     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

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.     

Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C3H6

Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.     

Ce/Zr系列催化剂上碳颗粒物燃烧行为

分别在TG和TPO上考察了CeO₂,ZrO₂及不同Ce/Zr比的CexZr1-xO₂固溶体催化剂上soot的燃烧性能,同时考察了反应气氛对活性的影响.结果表明:Ce基催化剂能明显降低soot的起燃温度,Ce/Zr比的不同导致Ce_xZr_1-xO₂催化剂性能的差异.反应的速度控制步骤随O₂浓度的不同而改变;H₂O对Ce_0.5Zr_0.5O₂上soot的氧化活性基本没有影响;由于NO氧化产生的NO₂具有更强的的氧化能力,因此NO对soot的燃烧具有促进作用,起燃温度降低了30℃.催化剂上的β氧种参与了soot燃烧过程.     

Performance and mechanism study for low-temperature SCR of NO with propylene in excess oxygen over Pt/TiO2 catalyst

A 0.5 wt.% Pt/TiO2 catalyst was prepared and used for the low-temperature selective catalytic reduction(SCR) of NO with C3 H6 in the presence of excess oxygen.The effects of Pt loading and O2 concentration on Pt/TiO2 catalytic performance for low-temperature SCR were investigated.It was found that optimal Pt loading was 0.5 wt.% and excess O2 favored low-temperature SCR of NOx.The mechanism of low-temperature SCR of NO with C3 H6 was investigated with respect to the behavior of adsorbed species over Pt/TiO2 at 150°C using in situ DRIFTS.The results indicated that surface nitrosyl species(Pt δ+-NO and Ti 3+-NO) and Pt 2+-CO are main reaction intermediates during the interactions of NO,C3 H6 and O2.A simplified NO decomposition mechanism for the low-temperature SCR of NO with C3 H6 was proposed.     

Kinetics of selective catalytic reduction of NO by NH_3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH_3.The kinetics of the SCR reaction in the presence of O_2 was studied in this work.The results showed that the observed reaction orders were 0.74-0.99,0.01-0.13,and 0 for NO,O_2 and NH_3 at 350-450℃,respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst.The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N_2 and H_2O.Gaseous O_2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process.It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH_3.     

O3/H2O2降解水中扑灭通效能研究

利用拟一级降解速率常数表征O3/H2O2对扑灭通(Prometon)的氧化效能,探讨了n(H2O2)/n(O3)、pH值、水质和碳酸氢根离子对去除的影响,对有机氧化产物进行了气相和液相质谱分析,以离子色谱法测定了反应过程中产生的NO3-,在此基础上对扑灭通降解途径进行了研究.结果表明,扑灭通初始浓度2 mg.L-1,反应温度25℃,O3投量13 mg.L-1时,最佳反应条件为n(H2O2)/n(O3)=0.7,体系pH为7～8;扑灭通在自来水中的去除效果好于纯水;HCO3-浓度>50 mg.L-1时,对扑灭通的氧化有明显的抑制作用.液质和气质的分析结果表明扑灭通并未开环,氧化过程中扑灭通三嗪环支链上的2个异丙基首先被氧化脱去,离子色谱检测到的NO3-是三嗪环支链胺基氧化的产物.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

汽车尾气净化催化剂Ag/SAPO-34选择性催化还原NO

评价了Ag/SAPO-34分子筛催化剂选择性还原NO的活性,并运用漫反射红外光谱原位研究NO在Ag/SAPO-34催化剂上的选择性催化还原机理.结果表明Ag/SAPO-34有良好的低温活性,在氧气浓度为3.6%和温度为573K～673K时NO还原成N2的转化率达70%;催化剂活性随C3H6浓度的增加而升高,随空速的增加而稍有下降.基于漫反射红外光谱,认为反应机理为:NO、丙烯和氧反应,在Ag/SAPO-34催化剂上生成吸附的有机-氮氧化物,再由这些吸附物种分解成N₂,催化还原的关键是形成有机-氮氧化物中间体.氧的作用是充分促进丙烯活化以及增加NO_x吸附态含量,并且氧的存在是有效产生一系列中间物不可缺少的条件.     

Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods, and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350–400°C, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20–100 nm.     

ACF负载金属氧化物及尿素低温去除NO

以活性炭纤维(ACF)负载NiO以及NiO-CeO2制备了一系列催化剂,并在催化剂上负载尿素作为还原剂,研究其在30～120℃范围内的催化还原NO的活性.通过SEM、BET、XRD等表征实验选择性地对催化剂进行了理化特征研究.结果表明,3种不同质量分数的NiO催化剂中,5%NiO/ACF效率较低,10%NiO的催化剂活性以及活性稳定性较好,在90℃即可达到50%左右的NO净化效率,15%NiO/ACF的催化活性稳定性较差.在3种不同质量分数的NiO-CeO2/ACF催化剂中,5%NiO-5%CeO2/ACF的活性以及活性稳定性最好,在110℃可达到55%以上的NO净化效率.10%CeO2-5%NiO/ACF活性高于5%CeO2-10%NiO/ACF;活性金属的最佳负载量为10%,过多的负载量会引起催化剂比表面积的减少从而导致催化剂活性下降;金属氧化物是催化反应的活性中心.对10%CeO2/ACF、10%NiO/ACF和5%CeO2-5%NiO/ACF的研究显示,5%CeO2-5%NiO/ACF的催化活性最好,CeO2和NiO的协同作用使催化剂的活性优于2种单独负载的催化剂.本研究还对催化剂的低温催化机制进行了分析和讨论.