V_2O_5/WO_3-TiO_2催化剂对NO转化率和N_2O生成量的影响

采用V_2O_5/WO_3-Ti O_2作为脱硝催化剂,考察不同厂家载体,活性组分V_2O_5和助剂WO_3负载量对催化剂脱硝活性的影响。结果表明,不同厂家载体对催化剂低温活性影响较大,高温时影响不大;1.5V_2O_5/x WO_3-Ti O_2(x=6%,10%,15%)上NO转化率随着WO_3含量增加而升高,同时N_2O也随着WO_3含量增加而升高。     

WO_3掺杂对V_2O_5/TiO_2-SnO_2催化剂NH_3选择性催化还原NO_x的影响

采用共沉淀法制备TiO_2-SnO_2固溶体,浸渍法负载WO_3和V_2O_5得到一系列V_2O_5-(x%)WO_3/TiO_2-SnO_2脱硝催化剂。利用比表面积测定(BET)、X射线衍射(XRD)、原位漫反射傅里叶变换红外光谱(in situ DRIFTS)、程序升温脱附(NH_3-TPD)、高分辨率透射电子显微镜(HRTEM)等表征技术,结合脱硝性能测试,研究催化剂的表面特性、微观结构及脱硝活性。结果表明:V_2O_5-12%WO_3/TiO_2-SnO_2催化剂在250~400℃的温度窗口具有95%的NO_x转换率;随着WO_3负载量增加,催化剂比表面积有所减小;WO_3以无定形态存在于催化剂表面;催化剂表面Br?nsted酸中心强度随WO_3负载量增加逐渐增大,这是V_2O_5-(12%)WO_3/TiO_2-SnO_2催化剂具有最佳脱硝活性的主要原因。     

不同方法负载钨钒钛催化剂对催化氧化邻二氯苯的影响

钨钒钛催化剂是消除钢铁冶炼废气中的二噁英最好的催化剂,为了降低工业生产成本,并获得良好的催化效果,将实验室筛选出的钨钒钛催化剂负载到不同载体上,研究催化剂负载量及不同负载方法对降解邻二氯苯催化效率的影响。采用溶胶-凝胶-浸渍法和直接浸渍法在堇青石蜂窝陶瓷上负载V_2O_5/WO_3/TiO_2催化剂,用X射线衍射、扫描电镜和X射线能量色散谱对制备的催化剂进行表征,结果表明,直接浸渍法在堇青石蜂窝陶瓷上负载的V_2O_5/WO_3/TiO_2催化剂含量比溶胶-凝胶-浸渍法负载的含量高,粒度较小,表面光滑无缝隙,活性成分V和W分散较好,催化活性高,在(250～350)℃邻二氯苯去除率大于95%,直接浸渍法负载的催化剂与堇青石的最佳质量比为1:100。     

整体式催化剂MnO_X-CeO_2/Al_2O_3催化燃烧苯研究

利用浸渍法负载制备出MnOX-CeO2/Al2O3整体式催化剂,研究了活性组分的负载量、催化剂的焙烧温度及焙烧时间对催化剂活性的影响,从而确定了催化剂的最佳制备工艺。结果表明：当Mn的负载量（质量分数）为10%,催化剂焙烧温度为600℃,焙烧时间为3 h时,催化剂MnOX-CeO2/Al2 O3具有最好的催化活性,在250℃时使苯的转化率在90%以上,并且适合比较大的空速范围,因此催化剂MnOX-CeO2/Al2O3具有广泛的工业应用前景。     

SCR烟气脱硝催化剂再生与回收处理可行性研究

将要失效的SCR脱硝催化剂,经过清洗,酸洗、活性负载和高温焙烧等工艺过程回收处理后再生,得到性能优越的脱硝催化剂,活性恢复到90%以上。对于无再生意义的催化剂,进行回收利用,利用焙烧、浸出工艺提取活性金属,得到TiO_2、V_2O_5、WO_3,回收率达到90%以上。实现了资源的综合利用,降低了生产成本,减少了环境污染。     

V_2O_5-MoO_3/TiO_2基催化剂煅烧颜色差异的研究

V_2O_5-MoO_3/TiO_2基催化剂是SCR脱硝系统的重要组成部分。通过实验探究了相同原料在制备催化剂工艺中出现颜色不一现象的原因。结果发现,不同价态钒氧化物的存在会导致煅烧后催化剂颜色的变化,通过在催化剂煅烧过程中增加与O_2的接触,促使高价态钒的生成,能够改善这一问题,使催化剂颜色均一。     

负载型Mn-Fe/γ-Al2O3低温脱硝催化剂的性能

采用共沉淀法制备了负载型Mn-Fe/γ-Al₂O₃低温SCR催化剂,运用固定床催化反应器,以氨气为还原剂,考察了负载量、活性组分配比、焙烧温度等制备条件和空速、O₂体积分数、NH₃/NO摩尔比等操作条件对Mn-Fe/γ-Al₂O₃催化剂低温脱硝性能的影响,并通过X射线衍射仪(XRD)、比表面积测定仪(BET)等手段对催化剂进行表征.结果表明,负载质量分数为20%、n(Mn):n(Fe)=4:1、焙烧温度为600℃、空速为16000h^-1、O₂体积分数为4%、NH₃/NO摩尔比为1.2、反应温度为200℃的条件下,NO转化率达到了96%以上.     

燃煤电厂废V_2O_5-WO_3/TiO_2催化剂中钒的回收研究进展

对于失活的SCR脱硝催化剂,回收再利用技术有着重要的社会、环保和经济价值。目前,燃煤电厂用的最多的商用SCR脱硝催化剂为V_2O_5-WO_3/TiO_2脱硝催化剂。介绍了对废V_2O_5-WO_3/TiO_2脱硝催化剂中的钒元素的回收工艺及原理,并对SCR脱硝催化剂回收再利用进行了展望。     

WO_3负载量对V_2O_5/WO_3-TiO_2催化剂脱硝性能的影响

采用V_2O_5/WO_3-TiO_2作为脱硝催化剂,考察活性组分V_2O_5和助剂WO_3负载量对催化剂脱硝活性和抗硫抗水性能的影响。结果表明,3%V_2O_5/x WO_3-TiO_2催化剂(x=3%、4%、5%、6%、7%、8%、9%、10%)上NOx转化率随着WO_3负载量增加而升高,催化剂反应温度窗口不断拓宽。单独通水蒸汽及同时通SO2和水蒸汽对催化剂的毒害作用均较强,表明H2O和NH3的竞争吸附是催化剂抗硫抗水性能较差的重要原因。SO_2与H_2O和NH_3反应生成亚硫酸铵盐和硫酸铵盐,导致催化剂孔隙堵塞,催化活性降低。     

制备参数对Mn-Ce-W/TiO2催化剂脱硝性能的影响

采用浸渍法制备了一系列Mn-Ce-W/TiO2催化剂,研究分析了一步浸渍和分步浸顺序、W含量、焙烧温度等制备参数对催化剂脱硝性能的影响.结果表明:添加W有助于稳定TiO2晶体结构,提高TiO2的相变温度,从而抑制TiO2由锐钛矿型向金红石型的转变,提高催化剂的脱硝效率.浸渍顺序应先钨后Mn、Ce,W的添加量为5%,在450 ℃焙烧得到的催化剂的脱硝效率最佳.     

水热处理和钨添加对低钒催化剂高温脱硝性能的影响

利用真空过量浸渍法在TiO₂和WO₃-TiO₂载体上负载0.5%钒（质量分数）制备了V₂O₅-TiO₂ （VTi）和V₂O₅/WO₃-TiO₂（VWTi）催化剂,并在含有10%（体积分数）水蒸气的空气氛下750℃水热处理24h得到处理态的VTi-A和VWTi-A催化剂。研究了水热老化和钨掺杂对催化剂脱硝效率的影响,并通过XRD、TEM、NH₃-TPD、H₂-TPR、XPS和Raman等表征方法对催化剂的结构和表面特性进行了表征分析。研究表明,水热处理和钨的协同作用使催化剂中产生更多的聚合态VO_x和低价态钒（V⁴⁺+V³⁺）。这两类活性物质所含有的氧物种具有较强SCR反应活性,可改善VWTi催化剂的高温脱硝性能,即使在酸性位数量减少的情况下仍有提升,这是低钒含量催化剂可满足燃气机组高温脱硝需求的主要原因。     

Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia

The physico-chemical characteristics and the reactivity of sub-monolayer V₂O₅-WO₃/TiO₂ deNO_x catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO₂ surface. The presence of tungsten oxide stabilizes the surface V^IV and modifies the redox properties of V₂O₅/TiO₂ samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V₂O₅-WO₃/TiO₂ catalysts exhibits higher activity than the binary V₂O₅/TiO₂ and WO₃/TiO₂ reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.     

Characterization by solid state V NMR spectroscopy

The fresh catalyst V₂O₅–WO₃/TiO₂ and catalyst used in SCR for 9000 h have been studied by the solid state ⁵¹V NMR spectroscopy in static and MAS conditions. According to ⁵¹V NMR in both samples the majority of vanadium sites are in a distorted octahedral environment similar to that in V₂O₅. There is a strong interaction between vanadium oxide and the support, but the concentration of vanadium atoms strongly bound to the surface is very small and can be detected only in MAS NMR experiments or after removing the excess of V₂O₅. There is no influence of WO₃ additives on the structure of the particles of V₂O₅, whereas the influence on the structure of strongly bounded V cannot be excluded. Combination of static (wide line) and MAS NMR techniques permit the characterization of not only the structure of the vanadium species but also small changes in their local environment. Hence these experiments show that there are some distortions of the local environment of vanadium sites of the vanadium oxide particles compared with the polycrystalline V₂O₅; treatment by SCR increases these distortions.     

含钛高炉渣制备SCR烟气脱硝催化剂

以含钛高炉渣为原料,稀硫酸为溶剂提取钛液,钛液经水解、高温焙烧后制得高比表面积的TiO₂,并以其为载体采用分步浸渍法制备了V₂O₅-WO₃/ TiO₂催化剂。优化了含钛高炉渣的酸解条件,对所得TiO₂进行了XRD、XRF、BET表征,用自制催化剂评价系统考察了所制备催化剂的脱硝性能及抗硫抗水性能。结果表明：H₂SO₄浓度40%、酸渣比1.5、酸解温度80℃、酸解时间3 h条件下,TiO₂浸出率可达90%,水解产物主要为锐钛型TiO₂,纯度达到74%,含有21.2%无定形SiO₂及少量其他杂质。SiO₂的存在提高了产物的比表面积、孔径,有利于活性组分的负载。以含钛高炉渣基TiO₂为原料制备的V₂O₅-WO₃/TiO₂脱硝催化剂相比于以商业TiO₂和TiOSO₄制备的催化剂,在250～450℃具有更高的催化活性,且在300℃具有较好的抗硫抗水性能。     

邻二氯苯在钒-钨-钛催化剂上的完全催化氧化

采用等体积浸渍法制备不同系列钒-钨-钛催化剂,以与二噁英TCDD化学结构式相似的邻二氯苯作为替代物,研究催化剂对邻二氯苯的去除效率,考察钒负载质量分数和钨负载质量分数对邻二氯苯催化氧化性能的影响,通过XRD和催化剂比表面积分析对催化剂的微观结构进行表征。结果表明,随着钒负载质量分数的增加,催化剂比表面积降低,催化剂性能降低;随着钨负载质量分数的增加,催化剂比表面积增加,催化剂性能提高。钨的加入有利于促进活性钒的分散,提高催化剂的比表面积,催化剂比表面积是影响催化剂性能的关键因素。     

溶胶-凝胶原位合成宽活性温度V2O5/TiO2脱硝催化剂

利用溶胶-凝胶技术原位合成一系列不同V₂O₅担载量的V₂O₅/TiO₂催化剂,通过BET、XRD、NH₃-TPD及紫外-可见光等手段对催化剂进行表征。结果表明：制备的催化剂均具有介孔结构,V₂O₅在TiO₂表面高度分散,且存在3种典型的酸性位。通过选择性催化还原反应对V₂O₅/TiO₂催化剂进行活性评价,结果显示随着V₂O₅含量的增加,NO转化率大于75%的温度窗口向低温方向偏移,含10% （质量分数）V₂O₅的催化剂的NO转化率为80%的温度窗口最宽为200～450℃,240℃时20 h连续实验表现出稳定的抗硫抗水性能。结合紫外-可见光谱分析,揭示了钒掺杂所形成的单聚和低聚钒酸盐为催化剂的活性组分。     

Investigation of the ammonia adsorption on monolithic SCR catalysts by transient response analysis

The adsorption of ammonia on three different monolithic SCR catalysts was investigated experimentally. Two of the examined monoliths were coated cordierite honeycombs, containing either V₂O₅–WO₃/TiO₂ or V₂O₅/TiO₂ as active components. The third sample was a commercially available extruded monolithic honeycomb consisting of V₂O₅–WO₃/TiO₂, and was tested for comparison. Different transient response methods and a modified temperature programmed desorption (TPD) method were used to investigate the ammonia adsorption in the presence of water (5%) and oxygen (10%). Under typical SCR conditions (stoichiometric ratio NH₃:NO<1), the ammonia coverage of the WO₃-free catalyst sample was significantly lower. Ammonia is more strongly adsorbed on the WO₃-containing catalyst. The extruded catalyst adsorbed substantially larger amounts of ammonia especially at low temperatures, leading to a slow response under transient conditions.     

Effect of promoters including tungsten and barium on the thermal stability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

The effect of tungsten and barium on the thermal stability of V₂O₅/TiO₂ catalyst for NO reduction by NH₃ was examined over a fixed bed flow reactor system. The activity of V₂O₅/sulfated TiO₂ catalyst gradually decreased with respect to the thermal aging time at 600 °C. The addition of tungsten to the catalyst surface significantly enhanced the thermal stability of V₂O₅ catalyst supported on sulfated TiO₂. On the basis of Raman and XRD measurements, the tungsten on the catalyst surface was identified as suppressing the progressive transformation of monomeric vanadyl species into crystalline V₂O₅ and of anatase into rutile phase of TiO₂. However, the NO removal activity of V₂O₅/sulfated TiO₂ catalyst including barium markedly decreased after a short aging time, 6 h at 600 °C. This may be due to the transformation of vanadium species to inactive V–O–Ba compound by the interaction with BaO which was formed by the decomposition of BaSO₄ on the catalyst surface at high reaction temperature of 600 °C. The addition of SO₂ to the feed gas stream could partly restore the NO removal activity of thermally aged V₂O₅/sulfated TiO₂ catalyst containing barium.     

Polyfunctionality of DeNOx catalysts in other pollutant abatement

The total oxidation of o-dichlorobenzene over differently loaded V₂O₅/TiO₂-based catalytic materials was studied. A series of vanadium-supported catalysts have been prepared, by incipient wetness impregnation, on different commercial supports (bare TiO₂, TiO₂/WO₃ and TiO₂/WO₃/SiO₂). The prepared materials were characterized by XRD, H₂-TPR, Raman spectroscopy and surface area measurements. All the catalysts exhibited high oxidation activity and the content of vanadium in the system was demonstrated to be important in controlling the catalyst activity and selectivity. Isolated and well-dispersed vanadium sites resulted beneficial for o-DCB conversion. Thus, in spite of the lower ability of SiO₂ to spread metal oxides the higher resistance to sintering of silica-containing materials also at high vanadium content, favors VO_x dispersion and leads to superior catalytic performance. Nevertheless, the presence of tungsten on the support and of high amount of vanadium also lead to the formation of partial oxidation products. In particular, dichloromaleic anhydride was formed and its production seems to be connected to the distribution of acidic sites.