The reactivity of V2O5-WO3-TiO2 catalyst supported on a ceramic filter candle for selective reduction of NO

For realizing the environmental issues and constituting an economical treatment system, a catalytic filter based on V₂O₅/TiO₂ supported on tubular filter elements has many advantages by removing NO_x and particulate simultaneously from flue gas. In order to improve the activity of a catalytic filter based on V₂O₅/TiO₂ supported on a commercial high temperature filter element (PRD-66), the promoting effects of WO₃ were investigated in an experimental unit. PRD-66 presented very good properties for SCR catalyst carrier since it contains much active material such as A1₂O₃ SiO{om2}, and MgO whose contributions were remarkable. For additional catalyst carrier, TiO₂ particles were coated in the pores of PRD-66 with relatively good distribution of the particle size less than 1 μm, by a coating process applying centrifugal force. WO₃, in the V₂O₅-WO₃-TiO₂/PRD-66 catalytic filter system, increased the SCR activity significantly and broadened the optimum temperature window. The catalytic filter shows the maximum NO conversion of more than 95% for NO concentration of 700 ppmv at face velocity of 0.02 m/sec, which is comparable to the current commercial catalytic filters of plate form.     

Pt-V2O5-WO3/TiO2 catalysts supported on SiC filter for NO reduction at low temperature

The catalytic filter, V₂O₅-WO₃-TiO₂ supported on a ceramic filter, is known as a promising material for treating particulates and NO _x simultaneously at optimum temperatures around 320°C. In order to improve its catalytic activity at low temperatures, the effect of Pt addition on the catalytic filter has been investigated. Catalytic filters, Pt-V₂O₅-WO₃-TiO₂/SiC, were prepared by co-impregnation of Pt, V, and W precursors on TiO₂ coated-SiC filter by vacuum aided-dip coating. The Pt-added catalytic filter shifted the optimum working temperature from 280–330°C (for the non Pt-impregnated filter) to 180–230°C, providing N _x slip concentration less than 20 ppm for the treatment of 700 ppm NO at a face velocity of 2 cm/s with the same value over the non Pt-added catalytic filters. The promotional effect following the addition of Pt is believed to result from electrical modification of the catalyst maintaining a high electron transfer state. Ammonia oxidation was also observed to be dominant above the optimal temperature for SCR.     

SO2 oxidation over the V2O5/TiO2 SCR catalyst

The effects of V₂O₅ loading of the V₂O₅/TiO₂ SCR catalyst on SO₂ oxidation activity were examined by infrared spectroscopy (DRIFT) and SO₂ oxidation measurement. Vanadium oxide added to the catalyst was found to be well dispersed over the TiO₂ carrier until covered with monolayer V₂O₅. The rate of SO₂ oxidation increased almost linearly with V₂O₅ loading below the monolayer capacity and attained saturation with further increase. The hydroxyl groups bonded to vanadium atoms, V–OH, might be altered by SO₂ oxidation. Both V=O and V–OH groups are likely involved in the adsorption and desorption of SO₂ and SO₃.     

Low temperature selective catalytic reduction of NO by NH3 over V2O5 supported on TiO2–SiO2–MoO3

The V₂O₅ catalysts supported on TiO₂–SiO₂–MoO₃ (TSM) prepared by the coprecipitation method were investigated for the selective catalytic reduction (SCR) of NO by NH₃ at low temperatures. The V₂O₅/TSM catalyst with 7–13 wt% SiO₂ was found to exhibit a superior SCR activity and a good sulfur tolerance at low temperatures (<250 °C). The presence of highly active polymeric vanadates formed by the incorporation of MoO₃ to TiO₂–SiO₂ and superior redox properties seems to enhance SCR activity, and furthermore the very lower SO₂ oxidation activity due to the higher acidity leads to the remarkable improvement of sulfur tolerance.     

The reduction behavior of Mo/TiO2-Al2O3 catalyst

The effect of TiO₂ modified Al₂O₃ surface on the reducibility of MoO₃ has been studied by TPR and XPS. The results show that Mo⁶⁺ in Mo/TiO₂-Al₂O₃ can be reduced to much lower valency, especially at low Mo loading. The influence of the calcination temperature on the reduction of Mo⁶⁺ on Al₂O₃ and TiO₂-Al₂O₃ carriers is different. The data reveals that the reducibility of Mo⁶⁺ on Al₂O₃ slightly decreased, while that on TiO₂-Al₂O₃ increased when the calcination temperature was raised. It is suggested that the stronger tetrahedral site of the Al₂O₃ surface was first occupied by TiO₂ and main octahedral Mo⁶⁺ in polymeric species-; and a small crystalline MoO₃ formed on TiO₂-Al₂O₃, whereas the formation of tetrahedral Mo⁶⁺ species and Al₂(MoO₄)₃ phase was inhibited.     

Influence of the V2O5 Loading on the Structure and Activity of V2O5/TiO2 SCR Catalysts for Vehicle Application

In this paper the effect of the vanadium oxide loading on the surface vanadia structure and the activity as well as selectivity in the catalytic reduction of NO with NH₃ was studied for a V₂O₅/TiO₂ model system. A series of TiO₂ (WO _x stabilized anatase) supported vanadia catalysts with varying loadings were characterized by laser Raman spectroscopy, ⁵¹V MAS-NMR, V K XANES. To determine the acidic properties, DRIFTS measurements were done with pyridine adsorbed on the samples. The measurements indicate that with increasing active phase loading square pyramidal coordinated surface vanadia species are replaced by an amorphous highly dispersed vanadium oxide phase with a coordination like V₂O₅. In addition, the ratio of Brønsted to Lewis acid sites is shifted from a comparatively low to an equal level at high loadings. This structural change is accompanied by a clearly improved catalytic activity and selectivity.     

Catalytic Conversions of Polychlorinated Benzenes and Dioxins with Low-chlorine Using V2O5/TiO2

Chlorinated benzene, especially 1,2-dichlorobenzene (1,2-DCB), has been widely used as one of surrogate compounds of dioxin to find the noble methods to control dioxin. However, the relationship between the catalytic activity of dioxin surrogate compound and dioxin has not been understood quite well. In this work, we used a vanadium based catalyst (V₂O₅/TiO₂) to compare catalytic activity of chlorinated benzenes and dibenzo-p-dioxins with low-chlorine content using the lab-scale system. We investigated the catalytic conversions of low-chlorinated dioxins, [2-monochlorodibenzo-p-dioxin (2-MCDD), 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD)] and polychlorinated benzenes [1,2-DCB, 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), pentachlorobenzene (PeCB), hexachlorobenzene (HCB)] using a V₂O₅/TiO₂ catalyst to understand quantitative relationship between dioxin and benzene with the chlorination level. The catalytic decomposition of chlorinated aromatic compounds was following 1,2-DCB > 1,2,3,4-TeCB > 2-MCDD > PeCB ≥ 2,3-DCDD > HCB. It might be more reasonable that PeCB or HCB should be used as the dioxin surrogate compound rather than 1,2-DCB. Also, we investigated the effect of both O₂ content and space velocity (SV) on the catalytic decomposition of 1,2-DCB in the presence of V₂O₅/TiO₂ catalyst because these factors should be considered significantly in combustion facilities to control various pollutants. The decomposition of 1,2-DCB shows dependency on the SV while the effect of oxygen content on the catalytic decomposition is negligible in the range of 5–20%.     

Thermal Decomposition of Divanadium Pentoxide V2O5: Towards a Nanocrystalline V2O3 Phase

Thermal decomposition of V₂O₅ was studied by means of transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). Samples were heated in a specimen chamber of an electron microscope up to 600 °C in vacuum at 10^-7 Torr. TEM and EELS reveal a sequence of transformations from V₂O₅ via VO₂ to V₂O₃, which differs from the electron-beam-induced reduction of V₂O₅. The phase transformation does not proceed topotactically. Our observation reveals that the initial thermal decomposition of V₂O₅ to V₂O₃ is followed by a combination of diffusion, coalescence, and stabilization processes. Our experiments open a new way for the preparation of single-crystalline V₂O₃ nano-particles.     

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。     

Sorption of ethene and ethane on the V2O5(001)/TiO2(001) anatase interface

Simulation techniques have been employed to investigate the differences in the low energy adsorption configurations of ethene and ethane on the TiO₂ supported and unsupported V₂O₅(001) surface. We find that the ethene molecule approaches much closer to thesupported V₂O₅(001) surface which is reflected in the 40 kj mol^–1 higher adsorption energy. The low energy adsorption configuration located for ethane on the supported V₂O₅ shows that the molecule does not approach as close to the supported V₂O₅ surface as does ethene, resulting in the adsorption energy of ethane being 52 kJ mol^–1 lower than that of ethene on the supported V₂O₅ surface.     

负载型钒钛脱硝催化剂酸化处理与性能

以商业TiO₂为载体,采用浸渍法制备了V₂O₅-WO₃-TiO₂/SO₄^2-催化剂,考察了硫酸酸化载体TiO₂的顺序及硫酸酸化量对氨气选择性催化还原NO活性的影响,采用XRD、BET、FT-IR、TG-DTA、TPD等手段对催化剂进行了表征。BET表征结果表明,随着酸化处理的用酸量增大,催化剂表面积降低;但FT-IR、TG结果表明,增大酸化处理用硫酸量提高了硫酸根与钨之间的电子交互作用。程序升温的活性测试结果表明,硫酸酸化处理对催化剂活性具有促进作用,结合NH₃-TPD表征证实了具有酸化处理程序制备的催化剂可以增强表面酸性位,从而使催化剂具有高活性。     

Reactivity of V2O5/MgF2 Catalysts for the Selective Ammoxidation of 3-Picoline

V₂O₅/MgF₂ catalysts with V₂O₅ contents ranging from 2.1 to 15.7 wt% were prepared, and the influence of the V₂O₅ content of the V₂O₅/MgF₂ catalyst on the structure and activity for the ammoxidation of 3-picoline was investigated. XRD data indicate that V₂O₅ is in a highly dispersed state though segregation of V₂O₅ into tiny crystallites occurs at and above 8 wt% V₂O₅. The 3-picoline ammoxidation activity increased with an increase in V₂O₅ content due not only to the species arising out of interaction of V₂O₅ and MgF₂, but also to the presence of V₂O₅ microcrystals in the catalysts.     

Wire-mesh honeycomb catalysts for selective catalytic reduction of NO with NH3

Both flat and corrugated wire mesh sheets were coated with aluminum powder by using electrophoretic deposition (EPD) method. Controlled thermal sintering of coated samples yielded uniform porous aluminum layer with a thickness of 100 μm that was attached firmly on the wire meshes. Subsequent controlled calcination formed a finite thickness of Al₂O₃ layer on the outer surface of each deposited aluminum particles, which resulted in the formation of Al₂O₃/Al double-layered composite particles that were attached firmly on the wire surface to form a certain thickness of porous layer. A rectangular-shaped wire-mesh honeycomb (WMH) module with triangular-shaped channels was manufactured by packing alternately the flat sheet and corrugated sheet of the Al₂O₃/Al-coated wire meshes. This WMH was further coated with V₂O₅-MoO₃-WO₃ catalyst by wash-coating method to be applied for the selective catalytic reduction (SCR) of NO with NH₃. With an optimized catalyst loading of 16 wt%, WMH catalyst module shows more than 90% NO conversion at 240 °C and almost complete NO conversion at temperatures higher than 300 °C at GHSV 5,000 h⁻¹. When compared with conventional ceramic honeycomb catalyst, WMH catalyst gives NO conversion higher by 20% due to reduced mass transfer resistance by the existence of three dimensional opening holes in WMH.     

Effects of preparation methods for V<Subscript>2</Subscript>O<Subscript>5</Subscript>-TiO<Subscript>2</Subscript> aerogel catalysts on the selective catalytic reduction of NO with NH<Subscript>3</Subscript>

A series of V₂O₅-TiO₂ aerogel catalysts were prepared by the sol-gel method with subsequent supercritical drying with CO₂. The main variables in the sol-gel method were the amounts of V₂O₅ and when the vanadium precursor was introduced. V₂O₅-TiO₂ xerogel and V₂O₅/TiO₂ (P-25) were also prepared for comparison. The V₂O₅-TiO₂ aerogel catalysts showed much higher surface areas and total pore volumes than V₂O₅-TiO₂ xerogel and impregnated V₂O₅/TiO₂ (P-25) catalysts. The catalysts were characterized by N₂ physisorption, X-ray diffraction (XRD), FT-Raman spectroscopy, temperature-programmed reduction with H₂ (H₂-TPR), and temperature-programmed desorption of ammonia (NH₃-TPD). The selective catalytic reduction of NOx with ammonia in the presence of excess O₂ was studied over these catalysts. Among various V₂O₅-TiO₂ catalysts, V₂O₅ supported on aerogel TiO₂ showed a wide temperature window exhibiting high NOx conversions. This superior catalytic activity is closely related to the large amounts of strong acidic sites as well as the surface vanadium species with characteristics such as easy reducibility and monomeric and polymeric vanadia surface species. This work was presented at the 7 ^th Korea-China Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Promoting Effect of Pt Addition to V2O5/ZrO2 Catalyst on Reduction of NO by C3H6

The effect of Pt addition to a V₂O₅/ZrO₂ catalyst on the reduction of NO by C₃H₆ has been studied by FTIR spectroscopy as well as by analysis of the reaction products. Pt loading promoted the catalytic activity remarkably. FTIR spectra of NO adsorbed on the catalysts doped with Pt show the presence of two different types of Pt sites, Pt oxide and Pt cluster, on the surface. The amount of these sites depends on Pt contents and the catalyst state. Pt atoms highly disperse on the surface as Pt oxide at low Pt content, being aggregated into Pt metal clusters by increasing Pt amount or reducing the catalysts. The spectral behavior of V=O bands on the surface also supports the formation of Pt clusters. It is concluded that Pt promotes the NO–C₃H₆ reaction through a reduction–oxidation cycle between its oxide and cluster form.     

An XPS study of dispersion and valence state of TiO2 supported vanadium oxide catalysts

Monolayer vanadium species are mainly in the V(V) valence state, but with XPS a small fraction of V⁴⁺ species are identified. Prolonged analysis treatment increases the V⁴⁺ concentration. With increasing vanadium concentration, a monolayer coverage corresponding to 1 mg V₂O₅ per m² develops, and it contains additional layers with a thickness of about 250 Å at 4 mg V₂O₅ per m², covering 3% of its surface area.     

SO2 and NO removal from flue gas over V2O5/AC at lower temperatures — role of V2O5 on SO2 removal

Supporting V₂O₅ onto an activated coke (AC) has been reported to significantly increase the AC's activity in simultaneous SO₂ and NO removal from flue gas. To understand the role of V₂O₅ on SO₂ removal, V₂O₅/AC is studied through SO₂ removal reaction, surface analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) techniques. It is found that the main role of V₂O₅ in SO₂ removal over V₂O₅/AC is to catalyze SO₂ oxidation through a VOSO₄-like intermediate species, which reacts with O₂ to form SO₃ and V₂O₅. The SO₃ formed transfers from the V sites to AC sites and then reacts with H₂O to form H₂SO₄. At low V₂O₅ loadings, a V atom is able to catalyze as many as 8 SO₂ molecules to SO₃. At high V₂O₅ loadings, however, the number of SO₂ molecules catalyzed by a V atom is much less, due possibly to excessive amounts of V₂O₅ sites in comparison to the pores available for SO₃ and H₂SO₄ storage.     

Effect of the metal oxide loading on the activity of silica supported MoO3 and V2O5 catalysts in the selective partial oxidation of methane

Precipitated silica catalysts loaded with either MoO₃ (0.2–4.0 wt%) or V₂O₅ (0.2–5.3 wt%) have been studied in the selective partial oxidation of methane to formaldehyde with molecular oxygen at 520 °C. The functionality of the SiO₂ surface towards the formation of HCHO is significantly promoted by V₂O₅, while it is depressed by the MoO₃.     

Gas-phase elemental mercury capture by a V2O5/AC catalyst

Gas-phase elemental mercury (Hg⁰) capture by an activated coke (AC) supported V₂O₅ (V₂O₅/AC) catalyst was studied in simulated flue gas and compared with that by the AC. The study on the influences of V₂O₅ loading, temperature, capture time and flue gas components (O₂, SO₂, H₂O and N₂) shows that the Hg⁰ capture capability of V₂O₅/AC is much higher than that of AC. It increases with an increase in V₂O₅ loading and is promoted by O₂, which indicates the important role of V₂O₅ in Hg⁰ oxidation and capture; it is promoted slightly by SO₂ but inhibited by H₂O; it increases with an increase in temperature up to 150 °C when Hg desorption starts. X-ray photoelectron spectroscopy analysis and sequential chemical extraction experiments indicate that the main states of Hg captured on V₂O₅/AC are HgO and HgSO₄. Temperature programmed desorption experiments were also made to understand the stability of the Hg captured.     

制备方法对V_2O_5-WO_3/TiO_2选择性催化还原催化剂性能的影响

采用共沉淀法、溶胶-凝胶法和浸渍法制备了V2O5质量分数4%和WO3质量分数6%的V2O5-WO3/TiO2选择性催化还原催化剂,对比了3种方法制备的催化剂选择性催化还原NO性能。采用X射线衍射、热重、N2吸附-脱附和程序升温还原等对制备的V2O5-WO3/Ti O2催化剂的结构和性质进行表征,结果表明,共沉淀法制备的V2O5-WO3/TiO2催化剂具有更好的选择性催化还原NO活性和更大的比表面积,影响共沉淀法选择性催化还原NO活性的主要因素是催化剂的热稳定性、表面羟基数量、比表面积、粒径分布以及V、W与Ti之间的内在作用。