纳米V_2O_5/AC催化剂脱除烟气中NO的研究

以质量分数20%硝酸改性后的柱状活性焦(AC)为载体,通过负载水热法合成的带状纳米V2O5,制备出了带状纳米V2O5/AC催化剂(SV/AC)。将SV/AC和传统浸渍法制备出的V2O5/AC催化剂进行脱硝催化性能测试比较,实验结果表明:在烟道温度为200℃,空速为6 000 L/(kg·h),体积分数φ(NO)=0.05%,φ(NH3)=0.05%,φ(O2)=5%,N2为平衡气体,V2O5负载量(质量分数)为1%的条件下,SV/AC的脱硝率可达45.36%,较AC,NAC,V2O5/AC分别提高了39.5%,23.07%,8.04%。SEM和EDS发现SV/AC催化剂的表面孔隙结构较V2O5/AC,NAC,AC更为发达,BET显示SV/AC的微孔率可达61.9%,较AC,NAC,V2O5/AC分别增加了39.6%,4.3%,14.0%。在实验条件相同的情况下,研究了添加Cu,Fe,Mo,Ce的金属氧化物对带状纳米V2O5/AC催化剂脱除NO性能的影响。实验结果表明:添加了Fe2O3后的带状纳米V2O5/AC催化剂的脱硝性能最佳,在Fe2O3和纳米V2O5的负载量均为1.0%时,催化剂的脱硝率达到最大值,为49.72%,比SV/AC提高了4.36%。     

V_2O_5/AC中温SCR催化剂的制备及其脱硝性能研究

以廉价的活性炭为载体,负载1%V2O5,制备出了中温V2O5/AC催化剂,其脱硝率在350~400℃可达60%以上。采用低温N2吸附法和傅里叶红外光谱法对催化剂进行了表征。结果表明,负载V2O5导致催化剂的比表面积降低,但是有利于SCR(选择性催化还原)反应的中孔增多,因而脱硝率较AC增大。H2SO4、HNO3、HCl酸化可以增大V2O5/AC的脱硝率,其中HNO3酸化效果最好,在350~400℃脱硝率可达75%以上,其原因是增大了表面的含氧官能团。     

吸附NH3的活性焦脱除SO2的实验研究

对新鲜活性焦和吸附有NH3的活性焦脱除不同气氛中的SO2进行了实验研究。结果表明,当烟气中不含有H2O和O2时,SO2在新鲜活性焦表面的脱除主要是物理吸附。活性焦吸附NH3后,增加了焦表面的碱性,提高了活性焦对SO2的吸附能力。当烟气中含有H2O和O2时,SO2在新鲜活性焦表面的脱除包括吸附和表面反应。NH3吸附在焦表面,不仅与硫酸反应,而且焦表面碱性的增加对SO2的脱除有很大的促进作用。对活性焦样品X射线光电子能谱分析发现,NH3吸附在焦表面产生了含N官能团,此官能团增加了活性焦表面的碱性,对SO2的吸附及氧化具有促进作用。     

V2O5-WO3/TiO2-SiO2制备及其选择性催化还原脱硝活性

以硫酸氧钛和硅溶胶为原料,通过共沉淀法制备得到高比表面积的TiO2-SiO2复合氧化物(Ti/Si=1:1atom),并以此复合氧化物为载体用浸渍法制备了V2O5-WO3/TiO2-SiO2脱硝催化剂,考察了催化剂脱硝性能。结果表明,TiO2-SiO2复合氧化物载体出现较多的隧道孔,提高了载体的比表面积,同时Ti元素更易分布在复合氧化物的表面。相比较于纯TiO2,以复合氧化物为载体的V2O5-WO3催化剂表现出更好的活性温度窗口,催化剂表面酸性更强,催化剂对NH3的吸附性能更好,在低的NH3/NO摩尔比情况下(0.8～1.0mol?mol?1),仍然具有较好的脱硝活性,反应温度280～350℃时,脱硝率可达到98%。     

活性焦性质对V2O5／AC催化剂还原NOx的影响

考察了活性焦载体制备条件和性质对V2O5／AC催化剂选择催化还原NO的影响。结果表明,活性焦载体的表面积较大有利于V2O5／AC催化剂的SCR活性,但活性焦中的炭对V2O5／AC活性也有重要的影响。SO2的存在对V2O5／AC催化剂活性有显著的促进作用,但这与活性焦载体的活化条件和性质无关。     

K2O对MnOx/TiO2低温脱硝催化剂的中毒作用研究

实验通过溶胶-凝胶法制备了MnOx/TiO2脱硝催化剂,以KNO3作为K2O的前驱物模拟催化剂钾中毒,通过SEM,XRD,BET,XPS,NH3-TPD,DRIFTS方法对催化剂微观结构及性能进行表征.在SCR活性试验仪上研究不同含量的K2O对催化剂脱硝活性的影响,结果发现:K2O对于催化剂的毒性较强,随着添加量的增大,催化剂脱硝活性急剧下降,比表面积和孔容逐渐下降.NH3-TPD及DRIFTS结果表明K2O中毒后催化剂表面酸量大大减少,主要原因是K2O的K+与催化剂的活性酸性位结合从而阻碍了NH3在催化剂上的吸附,导致催化剂脱硝率大大下降.     

立方相纳米氧化锆基催化剂脱硝机理研究

以纳米c-ZrO2为载体,用浸渍法制备出MnOx-CeO2/c-ZrO2催化剂,考察了组分负载量、反应温度对催化剂NH3-SCR脱硝活性影响,探讨了催化剂表面织构特征,分析了催化剂脱硝活性机理.结果显示,增加活性组分负载量和反应温度,催化剂脱硝效率增加,100℃时,2.5％ MnOx-CeO2/c-ZrO2脱硝效率为65.3％,15％ MnOx-CeO2/c-ZrO2脱硝效率达97.9％.XRD、BET、XPS、H2-TPR表征结果表明,负载后催化剂表面织构对脱硝反应有利.NH3-TPD测试显示,MnOx-CeO2/c-ZrO2催化剂表面Lewis酸位为强酸性位,NH3吸附在Lewis酸性位形成配位态NH3,经生成NH2 NO最后分解为N2和H2O.     

Fe2O3/AC催化剂的低温选择性催化还原脱硝性能

以活性焦(AC)为载体、Fe2O3为活性组分,采用等体积浸渍法制备Fe2O3/AC催化剂,研究了Fe含量对Fe2O3/AC催化剂低温脱硝性能的影响. 结果表明,当Fe负载量为6wt%时能获得比其它负载量更佳的NOx转化率,尤其在240℃时NOx转化率达93.9%,当分别有120?10?6(vol) SO2和3.5vol H2O存在时,脱硝率分别稳定在约86%和74%;催化剂孔径≤4 nm,随Fe负载量增加,孔径呈增大趋势;催化剂较稳定;Fe主要以γ-Fe2O3分散在催化剂表面,负载适量Fe2O3使表面吸附氧Oβ和Fe3+增多,为催化剂提供更多活性位,提高了Fe2O3/AC催化剂的低温选择性催化还原脱硝活性.     

Ce改性Fe2O3/AC催化剂低温SCR脱硝性能

以活性焦(AC)为载体、Fe和Ce为活性组分,采用等体积浸渍法制备了Fe2O3/AC和Ce?Fe2O3/AC催化剂,研究了Fe含量及Ce掺杂对Fe2O3/AC催化剂低温脱硝性能的影响,并对催化剂进行了表征. 结果表明,当Fe负载量为6wt%时,Fe2O3/AC催化剂的NOx转化率最高,240℃下达93.9%. 掺杂Ce后Ce?Fe2O3/AC催化剂的催化效率明显提高,当质量比Ce:Fe=0.5:6时,NOx转化率较高,120~200℃下NOx转化率比负载6wt% Fe的催化剂提高了5%?20%,且抗硫性能较好,240℃下通入100?10?6(vol) SO2,NOx转化率稳定在94.1%. 掺杂少量Ce可使γ-Fe2O3均匀分散在催化剂表面,且表面吸附氧Oα比例增大,催化剂的还原性增强,促进了选择性催化还原反应进行.     

载体对V_2O_5-MoO_3/TiO_2催化剂表面性质及其选择性催化还原脱硝性能的影响

采用比表面积分别为101.86 m2·g-1(A)、86.37 m2·g-1(B)和7.78(C)m2·g-1(C)的TiO_2载体,通过分步浸渍法制备V2O5-Mo O3/TiO_2(A,B,C)选择性催化还原脱硝催化剂。在空速为10 000 h-1和氨氮体积比1.0条件下,以TiO_2(A)与TiO_2(B)为载体制备的催化剂脱硝活性在反应温度窗口(350~450)℃超过90%,且具有良好的高温抗硫中毒性能和相对较小的氨气氧化率。而以TiO_2(C)为载体制备的脱硝催化剂活性温度窗口窄,在350℃时获得的最高脱硝活性仅为73%,且对NH3的氧化作用较强。利用X射线衍射、低温N2吸附-脱附、紫外-可见漫反射光谱、H2程序升温还原和NH3程序升温脱附等对载体和催化剂进行表征。结果表明,活性组分V2O5在载体TiO_2(A)上分散性良好,主要以孤立态钒氧物种形式存在,因此,以TiO_2(A)为载体制备的催化剂比表面积、氧化还原性和表面酸性等性能更优。     

活性焦性质对V_2O_5/AC催化剂还原NO_X的影响

考察了活性焦载体制备条件和性质对Ｖ２Ｏ５／ＡＣ催化剂选择催化还原ＮＯ的影响．结果表明,活性焦载体的表面积较大有利于 Ｖ２Ｏ５／ＡＣ催化剂的 ＳＣＲ活性,但活性焦中的炭对 Ｖ２Ｏ５／ＡＣ活性也有重要的影响．ＳＯ２的存在对Ｖ２Ｏ５／ＡＣ催化剂活性有显著的促进作用,但这与活性焦载体的活化条件和性质无关．     

V2O5负载量对V2O5／TiO2催化剂SCR法脱硝的影响

以TiO2载体,采用浸渍法制备了不同V2O5负载量的用于选择性催化还原NOx的V2O5／TiO2催化剂。利用BET,SEM和Ⅺ①,对不同V2O5负载量的催化剂组成、结构、形貌和性能进行了表征,考察不同V2O5负载量对催化剂制备的影响。结果表明制备的催化剂具有较多的中孔和微孔,催化剂中V2O5含量的增加,会降低催化剂的表面积;V2O5含量为2％的V2O5／TiO2催化剂样品比表面积最大,但是其活性非常低;V2O5含量为4％催化剂比表面积较大,NOx脱转化率高;V2O5的负载量小时,V2O5主要以等轴聚合的钒基型式（V3O7和V6O13）存在,这些钒基是催化剂的活性中心;当负载量超过6％,V2O5主要以结晶相存在,占据大量活性位,降低催化效果。     

Carbon nanotubes loaded with vanadium oxide for reduction NO with NH3 at low temperature☆

The catalytic activity of carbon nanotubes-supported vanadium oxide (V2O5/CNTs) catalysts in the selective catalytic reduction (SCR) of NO with NH3 at low temperatures (≤250 °C) was investigated. The effects of V2O5 loading, reaction temperature, and presence of SO2 on the SCR activity were evaluated. The results show that V2O5/CNTs catalysts exhibit high activity for NO reduction with NH3 at low-temperatures. The catalysts also show very high stability in the presence of SO2. More interestingly, their activities are significantly promoted in-stead of being poisoned by SO2. The promoting effect of SO2 is distinctly associated with V2O5 loading, particularly maximized at low V2O5 loading, which indicated the role of CNTs support in this effect. The promoting effect of SO2 at low temperatures suggests that V2O5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.     

制备条件对柴油车用V2O5-WO3/TiO2催化剂催化性能的影响

采用偏NH4VO3和TiO2为前驱体制备选择性催化还原(SCR)催化剂涂层所需浆料,分别以分步涂覆法和一步涂覆法将浆料浸涂在蜂窝陶瓷载体上,得到了整体涂覆式选择性催化还原催化剂.对草酸添加量、焙烧时间及V2O5含量对催化活性的影响进行了研究,结果表明,V2O5(4%)-WO3/TiO2(450℃,3 h)和V2O5(5...     

V2O5-MoO3/TiO2 催化剂的NOx选择性催化还原及SO2氧化活性

采用浸渍法以TiO₂为载体制备V₂O₅-MoO₃/TiO₂ 选择性催化还原催化剂,研究V₂O₅和MoO₃负载量对于催化剂选择性催化还原反应及SO₂氧化活性的影响,并考察氧含量、氨氮物质的量比和反应空速对3%V₂O₅-6%MoO₃/TiO₂催化剂选择性催化还原脱硝活性的影响。结果表明,随着催化剂中V₂O₅负载质量分数增加,V₂O₅-MoO₃/TiO₂ 催化剂的选择性催化还原活性和SO₂氧化活性均呈上升趋势。MoO₃的负载对催化剂的SO₂氧化活性有明显抑制作用。MoO₃负载质量分数超过9%,制备的催化剂既保持较高的低温选择性催化还原活性,又使选择性催化还原反应中的SO₂转化率小于1%。     

DRIFTS investigation of V=O behavior and its relations with the reactivity of ammonia oxidation and selective catalytic reduction of NO over V2O5 catalyst

The behavior of V=O band over V₂O₅ crystallite during NH₃ adsorption and SCR reaction was characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and the results are correlated with the reactivity in NH₃ oxidation and SCR reaction. It is found that the decrease of V=O band intensity is due either to the reduction of V₂O₅ surface and/or to the adsorption of ammonia. The 70% intensity of original V=O band is preserved up to 573 K under the conditions of SCR reaction. The vanadium oxidation state is about +4.4. When the temperature reached 673 K, almost all the V=O band was recovered. From these results, it can be suggested that the decrease of the apparent SCR activity due to the increase of NO amount through NH₃ oxidation above 673 K be attributed to the increase of two neighboring V=O sites, which favor the NO formation in ammonia oxidation.     

NO–NH3 coadsorption on vanadia/titania catalysts: determination of the reduction degree of vanadium

Diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) has been used to study NH₃ and NO adsorption over a 15% w/w vanadia/titania catalyst. NH₃ is adsorbed as coordinate NH₃ and NH₄⁺ species over the oxidised catalyst, leading to the reduction of the vanadia surface. At 300°C, adsorbed nitrosyls species are detected, suggesting that the oxidation of gaseous or adsorbed ammonia species takes place over the V=O sites. Coadsorption experiments show that NO is able to reoxidise about the 57% of the reduced V=O groups, resulting in N₂, according to a NO+V_□→1/2N₂+V=O reaction. On the other hand, NO is only adsorbed over vanadia reduced surfaces. The measure of the area of the 2ν(V=O) bands results in an estimate of the oxidation state of vanadium. From this estimate it can be concluded that nitrosyls species are adsorbed on the catalyst surface for vanadium atoms having an oxidation state ranging from +4 to +3.1.     

原位漫反射红外光谱研究NO和NH3在CuO/γ-Al2O3催化剂上的吸附行为

利用原位漫反射红外光谱法在线研究NH₃和NO在CuO/γ-Al₂O₃催化剂表面吸附和氧化的反应过程。NH₃不仅能被吸附在L酸位,也能被吸附在B酸位。NH3氧化脱氢形成NH₂物种是反应的中间步骤。NO和NO₂以多种形态吸附在催化剂表面。O₂存在条件下有利于吸附的NO物种被氧化成高价的NO₂。暂态实验中,吸附NH₃饱和的催化剂载体通入NO和O₂后,共价吸附的NH₃首先消失,而NH⁺₄没有参加反应。吸附NO饱和的催化剂载体通入NH₃和O₂后,吸附态NO特征峰基本没有变化。选择性催化还原反应发生在吸附态NH₃和气态NO之间,吸附态的NO及其氧化生成的亚硝基和硝基物种不参与SCR反应。     

SCR反应过程中NO/NH3在γ-Al2O3表面吸附特性

采用密度泛函理论（DFT）方法研究了NO和NH₃在完整和有缺陷的γ-Al₂O₃（110）表面吸附与SCR（选择催化还原）反应特性。研究表明,NO在完整的（110）表面的吸附作用较弱,而NH₃分子的吸附作用较强,NH₃分子在Al原子顶位可形成稳定吸附。反应路径研究结果表明完整的（110）表面上SCR反应的决速步为-NH₂NO基团的分解,反应的最大能垒为235.75 kJ·mol^-1。对于产生氧空穴的有缺陷（110）表面,NO和NH₃均可稳定吸附,NH₃在吸附过程中可直接裂解成NH₂和H。另外,SCR反应在有缺陷（110）表面的最大能垒明显较低,说明氧空穴的存在促进了SCR脱硝反应的进行。     

Competition between NO reduction and NO decomposition over reduced V–W–O catalysts

The SCR of NO and NO decomposition were investigated over a V–W–O/Ti(Sn)O₂ catalyst on a Cr–Al steel monolith. The conversions of NO and NH₃ over the reduced and oxidised catalysts were determined. The higher conversion of NO than of NH₃ was observed in SCR over the reduced catalyst and very close conversions of both substrates were found over the oxidised one. The increase of the pre-reduction temperature was found to cause an increase in catalyst activity and its stability in direct NO decomposition. The surface tungsten cations substituted for vanadium ones in vanadia-like active species are considered to be responsible for the direct NO decomposition. The results of DFT calculations for the 10-pyramidal clusters: V₁₀O₃₁H₁₂ (V–V) and V₉WO₃₁H₁₂ (V–W) modelling (0 0 1) surfaces of vanadia and WO₃–V₂O₅ solid solution (s.s.) active species, respectively, show that preferable conditions for NO adsorption exist on W sites of s.s. species and that reduction causes an increase in their ability for electron back donation to the adsorbed molecule. Electron back donation is believed to be responsible for the electron structure reorganisation in the adsorbed NO molecule resulting in its decomposition. The high selectivity of NO decomposition to dinitrogen was considered to be connected with the formation of the tungsten nitrosyl complexes solely via the W–N bond.