SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

A practical scale evaluation of sulfated V2O5/TiO2 catalyst from metatitanic acid for selective catalytic reduction of NO by NH3

The characteristics of sulfated V₂O₅/TiO₂ honeycomb catalyst from metatitanic acid (MTA) were studied in the practical conditions of pilot plant using high dust flue gas from coal fired utility boiler. The effects of reaction temperature, NH₃/NO mole ratio, space velocity and operation time on the reduction of nitric oxide (NO) were mainly investigated for engineering application. The catalyst showed high NO reduction of about 90% at a space velocity of 4000 h⁻¹, NH₃/NO mole ratio of 1.0 and reaction temperature of 300–400 °C. The efficiency of this catalyst remained constant during the present experiment of 2400 h and the erosion by fly ash was lower than that of the commercial catalysts. These results clearly demonstrate the high potential for this catalyst to be applied commercially for the control of NO_x emissions from coal fired utility boiler.     

Inhibition effect of H2O on V2O5/AC catalyst for catalytic reduction of NO with NH3 at low temperature

The inhibition effect of H₂O on V₂O₅/AC catalyst for NO reduction with NH₃ is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H₂O does not reduce NO and NH₃ adsorption on V₂O₅/AC catalyst surface, but promotes NH₃ adsorption due to increases in Brønsted acid sites. Many kinds of NH₃ forms present on the catalyst surface, but only NH₄⁺ on Brønsted acid sites and a small portion of NH₃ on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH₃ on Lewis acid sites does not react with NO, regardless the presence of H₂O in the feed gas. H₂O inhibits the SCR reaction between the NH₃ on the Lewis acid sites and NO, and the inhibition effect increases with increasing H₂O content. The inhibition effect is reversible and H₂O does not poison the V₂O₅/AC catalyst.     

Improvement of response characteristics of TiO2 humidity sensors by simultaneous addition of Li2O and V2O5

Porous TiO₂ ceramics were prepared by adding various amounts of Li₂O and V₂O₅ and the humidity sensitivity of the resulting ceramics was investigated by means of electrical measurements, scanning electron microscopy and mercury intrusion porosimetry. Simultaneous addition of Li₂O and V₂O₅ to TiO₂ enabled sintering at temperatures as low as 700 °C and also decreased the impedance of the ceramics. Furthermore, in the ceramics including these additives simultaneously, excellent humidity sensitivity as well as good response characteristics were observed. The microstructures of these ceramics depended on the firing temperature and the amount and ratio of Li₂O/V₂O₅, and optimum humidity sensitivity was observed for the sample including both 0.25 mol% Li₂O and 0.75 mol% V₂O₅ fired at 700 °C. These results indicated that the humidity sensitivity and its response characteristics were closely related to the microstructure, and that improving the uniformity of microstructure is important for improving humidity sensitivity and its response characteristics.     

Catalytic activation of ceramic filter elements for combined particle separation, NOx removal and VOC total oxidation

The development of a catalytically active filter element for combined particle separation and NO_x removal or VOC total oxidation, respectively, is presented. For NO_x removal by selective catalytic reduction (SCR) a catalytic coating based on a TiO₂–V₂O₅–WO₃ catalyst system was developed on a ceramic filter element. Different TiO₂ sols of tailor-made mean particle size between 40 and 190 nm were prepared by the sol–gel process and used for the impregnation of filter element cylinders by the incipient wetness technique. The obtained TiO₂-impregnated sintered filter element cylinders exhibit BET surface areas in the range between 0.5 and 1.3 m²/g. Selected TiO₂-impregnated filter element cylinders of high BET surface area were catalytically activated by impregnation with a V₂O₅ and WO₃ precursor solution. The obtained catalytic filter element cylinders show high SCR activity leading to 96% NO conversion at 300 °C, a filtration velocity of 2 cm/s and an NO inlet concentration of 500 vol.-ppm. The corresponding differential pressures fulfill the requirements for typical hot gas filtration applications. For VOC total oxidation, a TiO₂-impregnated filter element support was catalytically activated with a Pt/V₂O₅ system. Complete oxidation of propene with 100% selectivity to CO₂ was achieved at 300 °C, a filtration velocity of 2 cm/s and a propene inlet concentration of 300 vol.-ppm.     

Combined effect of H2O and SO2 on V2O5/AC catalysts for NO reduction with ammonia at lower temperatures

Combined effect of H₂O and SO₂ on V₂O₅/AC the activity of catalyst for selective catalytic reduction (SCR) of NO with NH₃ at lower temperatures was studied. In the absence of SO₂, H₂O inhibits the catalytic activity, which may be attributed to competitive adsorption of H₂O and reactants (NO and/or NH₃). Although SO₂ promotes the SCR activity of the V₂O₅/AC catalyst in the absence of H₂O, it speeds the deactivation of the catalyst in the presence of H₂O. The dual effect of SO₂ is attributed to the SO₄²⁻ formed on the catalyst surface, which stays as ammonium-sulfate salts on the catalyst surface. In the absence of H₂O, a small amount of ammonium-sulfate salts deposits on the surface of the catalyst, which promote the SCR activity; in the presence of H₂O, however, the deposition rate of ammonium-sulfate salts is much greater, which results in blocking of the catalyst pores and deactivates the catalyst. Decreasing V₂O₅ loading decreases the deactivation rate of the catalyst. The catalyst can be used stably at a space velocity of 9000 h⁻¹ and temperature of 250 °C.     

NO reduction with NH3 over chromia–vanadia catalysts supported on TiO2: an in situ Raman spectroscopic study

In situ Raman spectroscopy was used for studying the ternary 2% CrO₃–6% V₂O₅/TiO₂ catalyst, for which a synergistic effect between vanadia and chromia leads to enhanced catalytic performance for the selective catalytic reduction (SCR) of NO with NH₃. The structural properties of this catalyst were studied under NH₃/NO/O₂/N₂/SO₂/H₂O atmospheres at temperatures up to 400 °C and major structural interactions between the surface chromia and vanadia species are observed. The effects of oxygen, ammonia, water vapor and sulfur dioxide presence on the in situ Raman spectra are presented and discussed.     

Characteristics of V2O5 supported on sulfated TiO2 for selective catalytic reduction of NO by NH3

V₂O₅ supported on sulfated TiO₂ catalyst was investigated by using Raman and infrared spectroscopies to examine the surface structure of vanadia and the hydroxyl groups of titania along with the sulfate species on the catalyst surface. The surface structure of vanadia plays a critical role, particularly for the reduction of NO by NH₃. The polymeric vanadate species on the catalyst surface is the active reaction site for this reaction system. The surface sulfate species enhanced the formation of the polymeric vanadate by reducing the available surface area of the catalyst. The formation of the polymeric vanadate species on the catalyst surface also depends on the number of hydroxyl groups on the support. Both the sulfate and the vanadate species strongly interacted with the hydroxyl groups on titania. The fewer the number of the hydroxyl sites on the catalyst surface became by increasing the calcination temperatures, the more the polymeric vanadate species formed. A model was proposed to elucidate the progressive alteration of the surface structure of vanadia by the amounts of V₂O₅ loadings and the sulfate species on the catalyst surface.     

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.     

Dielectric behavior of Nb2O5-doped TiO2/epoxy thick films

TiO₂/epoxy composite thick films containing the TiO₂ powders doped with 4 and 10 vol% Nb₂O₅ heat treated under vacuum at 1050 and 1150 °C, were prepared by the screen printing and curing steps. The Nb₂O₅-doped TiO₂ ceramic bulks demonstrated a higher effective dielectric constant at different densification environments, as compared with pure TiO₂. The dielectric properties of the TiO₂/epoxy thick films were improved if the heat-treated 4 vol% Nb₂O₅-doped TiO₂ powder was incorporated instead of the un-doped and heat-treated 10 vol% Nb₂O₅-doped TiO₂ powders. The disadvantage of the doped TiO₂ having higher dielectric loss tangent could be minimized after its powder was properly treated and mixed with epoxy to form the TiO₂/epoxy composite. A best result with the dielectric constant of 23 and the loss tangent of 0.046 was obtained for the 40 vol% TiO₂/epoxy composite thick films, where the TiO₂ powder was doped with 4 vol% Nb₂O₅ followed by calcination at 1000 °C in air and heat treatment at 1150 °C under vacuum.     

Effects of microwaves on selective oxidation of toluene to benzoic acid over a V2O5/TiO2 system

Two series of catalysts, V₂O₅/TiO₂ and modified V₂O₅/TiO₂, were prepared with a conventional impregnation method. They were tested in the selective oxidation of toluene to benzoic acid under microwave irradiation. The reaction conditions were optimized over V₂O₅/TiO₂. It was found that in the microwave catalytic process the optimum reactor bed temperature of the titled reaction decreases to 500 K (600 K in the conventional process). The modification of V₂O₅/TiO₂ with MoO₃, WO₃, Nb₂O₅ or Ta₂O₅, which has no negative influence on the reaction in the conventional catalytic process, can greatly promote the catalytic activities in the microwave process, leading to a high yield of benzoic acid (41%). The effects of microwave electromagnetic field on the catalysts are discussed.     

A study of the deactivation by sulfur and regeneration of a model NSR Pt/Ba/Al2O3 catalyst

The deactivation by sulfur and regeneration of a model Pt/Ba/Al₂O₃ NO_x trap catalyst is studied by hydrogen temperature programmed reduction (TPR), X-ray diffraction (XRD), and NO_x storage capacity measurements. The TPR profile of the sulfated catalyst in lean conditions at 400 °C reveals three main peaks corresponding to aluminum sulfates (550 °C), “surface” barium sulfates (650 °C) and “bulk” barium sulfates (750 °C). Platinum plays a role in the reduction of the two former types of sulfates while the reduction of “bulk” barium sulfates is not influenced by the metallic phase. The thermal treatment of the sulfated catalyst in oxidizing conditions until 800 °C leads to a stabilization of sulfates which become less reducible. Stable barium sulfides are formed during the regeneration under hydrogen at 800 °C. However, the presence of carbon dioxide and water in the rich mixture allows eliminating more or less sulfides and sulfates, depending on the temperature and time. The regeneration in the former mixture at 650 °C leads to the total recovery of the NO_x storage capacity even if “bulk” barium sulfates are still present on the catalyst.     

Effect of calcination temperature on the low-temperature oxidation of CO over CoOx/TiO2 catalysts

A 5 wt% CoO_x/TiO₂ catalyst has been used to study the effect of calcination temperature on the activity of this catalyst for CO oxidation at 100 °C under a net oxidizing condition in a continuous flow type fixed-bed reactor system, and the catalyst samples have been characterized using TPD, XPS and XRD measurements. The catalyst after calcination at 450 °C gave highest activity for this low-temperature CO oxidation, and XPS measurements yielded that a 780.2-eV Co 2p_3/2 main peak appeared with this catalyst sample and this binding energy was similar to that measured with pure Co₃O₄. After calcination at 570 °C, the catalyst, which had possessed practically no activity in the oxidation reaction, gave a Co 2p_3/2 main structure peak at 781.3 eV which was very similar to those obtained for synthesized Co_nTiO_n+2 compounds (CoTiO₃ and Co₂TiO₄), and this catalyst sample had relatively negligible CO chemisorption as observed by TPD spectra. XRD peaks indicating only the formation of Co₃O₄ particles on titania surface were developed in the catalyst samples after calcination at temperatures ≥350 °C. Based on these characterization results, five types of Co species could be modeled to exist with the catalyst calcined at different temperatures. Among these surface Co species, the Type A clean Co₃O₄ particles were predominant on a sample of the catalyst after calcination at 450 °C and highly active for CO oxidation at 100 °C, and the calcination at 570 °C gave the Type B Co₃O₄ particles with complete Co_nTiO_n+2 overlayers inactive for this oxidation reaction.     

Sulfuric acid formation over ammonium sulfate loaded V2O5–WO3/TiO2 catalysts by DeNOx reaction with NOx

Operating the SCR DeNO_x reactor at temperatures below 200 °C results in a considerable saving in operating costs. Plant experience shows that on the catalysts in these second generation DeNO_x plants, even for flue gases with SO₂ concentration below 10 mg/m³, over 1–2 years operating time sizeable quantities of ammonium sulfates accumulate. Ammonium sulfates deposited on V₂O₅–WO₃/TiO₂ catalysts react with NO_x to nitrogen and sulfuric acid. Second-order rate constants of this reaction for temperatures of 170 °C have been derived. It could be shown that the sulfuric acid formed on the catalyst is displaced by water vapour and desorbs resulting in gas phase concentrations of up to 6.5 mg acid/m³ flue gas. Plant equipment downstream of the ammonium sulfate containing low temperature DeNO_x catalysts has to be protected against the corrosive action of the sulfuric acid in the flue gases leaving the DeNO_x reactor.     

V2O5-WO3-MoO3/TiO2催化剂用于NH3选择性还原减排NOx的性能（英文）

The V2O5-WO3-MoO3/TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM) and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass percentage of V:W:Mo:TiO2 :fiber glass= 1:4.5:4.5:72:18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to rutile by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3 . The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615-1640 mg·m-3 . Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.     

Catalytic activity and solid acidity of vanadium oxide thin layer loaded on TiO2, ZrO2, and SnO2

Vanadium oxide spread highly on TiO₂ (anatase, A) and SnO₂, and rather densely on TiO₂ (rutile, R) and ZrO₂ to make the monolayer in less than 4–5 V nm⁻². Profile of acid site of the monolayer was measured by temperature programmed desorption of ammonia, and its relation with the surface oxidation state was studied. The acid site density was high on the V₂O₅/TiO₂ (A) independent of the degree of oxidation. On the other hand, that of V₂O₅/TiO₂ (R) and V₂O₅/ZrO₂ depended on the oxidation state, and the high value of the concentration was observed on the oxidized one. The strength of acid site generated on the V₂O₅ monolayer on TiO₂ was as high as on the HZSM-5 zeolite. Turnover frequency (TOF) of propane conversion, and product selectivity were measured in propane oxidation. Among tested oxides, the V₂O₅/TiO₂ (A) showed the high TOF and selectivity to form propylene, while those loaded on TiO₂ (R) and ZrO₂ the small TOF and poor selectivity. Therefore, the reaction profile of activity and selectivity could be related with the extent of spreading and solid acidity. An idea of limit of the acid site density ca. 1.5 nm⁻² on the monolayer was elucidated.     

Catalytic performance of a novel ceramic-supported vanadium oxide catalyst for NO reduction with NH3

A novel TiO₂/Al₂O₃/cordierite honeycomb-supported V₂O₅–MoO₃–WO₃ monolithic catalyst was studied for the selective reduction of NO with NH₃. The effects of reaction temperature, space velocity, NH₃/NO ratio and oxygen content on SCR activity were evaluated. Two other V₂O₅–MoO₃–WO₃ monolithic catalysts supported on Al₂O₃/cordierite honeycomb or TiO₂/cordierite honeycomb support, two types of pellet catalysts supported on TiO₂/Al₂O₃ or Al₂O₃, as well as three types of pellet catalysts V₂O₅–MoO₃–WO₃–Al₂O₃ and V₂O₅–MoO₃–WO₃–TiO₂ were tested for comparison. The experiment results show that this catalyst has a higher catalytic activity for SCR with comparison to others. The results of characterization show, the preparation method of this catalyst can give rise to a higher BET surface area and pore volume, which is strongly related with the highly active performance of this catalyst. At the same time, the function of the combined carrier of TiO₂/Al₂O₃ cannot be excluded.     

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。     

EPR spectroscopic characterization of DeNOx and SO2 oxidation catalysts and model systems

The industrial SO₂ oxidation catalyst VK69 deactivates at around 440°C in a 10% SO₂, 11% O₂, 79% N₂ gas mixture. In situ EPR measurements show that the deactivation is caused by the precipitation of V(IV) compounds. DeNO_x catalysts based on V₂O₅/TiO₂, the TiO₂ support, analytical grade anatase and transition metal-exchanged Al-PILCs (pillared clay) have been characterized by EPR spectroscopy and the catalytic activity of the catalysts monitored up to 500°C. Depending on the exchanged metal ion, a relatively large temperature range for the catalytic activity towards the SCR reaction was observed.     

Direct NO decomposition over La2−xBaxNiO4 catalysts containing BaCO3 phase

Catalytic and in situ Fourier Transform Infrared (FTIR) spectroscopic studies were conducted to investigate the adsorption and oxidation of o- and p-chlorophenol over a 3.6 wt.% V₂O₅/TiO₂ catalyst. At a space velocity of approximately 53,000 cm³ g⁻¹ h⁻¹, this catalyst was found to be active for the oxidation of o- and p-chlorophenol at temperatures as low as 200 °C, yielding CO₂ and HCl as the main products. Trace amounts of higher molecular weight products were also detected at the reactor outlet indicating the operation of additional condensation, coupling and chlorination/dechlorination side reactions in parallel to the main complete oxidation scheme. The in situ FTIR studies revealed that different phenols adsorb on the V₂O₅/TiO₂ catalyst through their hydroxyl group. Furthermore, the formation of similar surface species (i.e., maleates, acetates, formates and an aldehyde-type species) was observed. The results were compared with those of previous studies on the oxidation of m-dichlorobenzene (m-DCB) and benzene and suggest that a similar reaction mechanism is operating in all cases, although the relative kinetic significance of the different steps varies with the presence and the position of the hydroxyl and chlorine groups on the aromatic ring.