A novel carbon-supported vanadium oxide catalyst for NO reduction with NH3 at low temperatures

A novel activated carbon-supported vanadium oxide catalyst was studied for SCR of NO with NH₃ at low temperatures (100 – 250°C). The effects of reaction temperature, preparation conditions and SO₂ on SCR activity were evaluated. The results show that this catalyst has a high catalytic activity for NO–NH₃–O₂ reaction at low temperatures. Preoxidation of the calcined catalyst helps improve catalytic activity. V₂O₅ loading, other than calcination temperature, gives a significant influence on the activity. SO₂ in the flue gas does not de-activate the catalyst but improves it. A stability test of more than 260 h shows that the catalyst is highly active and stable in the presence of SO₂.     

Low temperature SCR of NO with NH3 over carbon nanotubes supported vanadium oxides

A novel multiwalled carbon nanotube (CNTs) supported vanadium catalyst was prepared. The structure of catalyst prepared was characterized by TEM, BET, FTIR, XRD and temperature-programmed desorption (TPD) methods. The results indicated that vanadium particles were highly dispersed on the wall of carbon nanotubes. The V₂O₅/CNT catalysts showed good activities in the SCR of NO with a temperature range of 373–523 K. The Lewis acid sites on the surface of V₂O₅/CNT are the active sites for the selective catalytic reduction (SCR) of NO with NH₃ at low temperatures. It was suggested that the reaction path might involve the adsorbed NH₃ species reacted with NO from gaseous phase and as well as the adsorbed NO₂ species. The diameter of CNTs showed positive effect on the activities of the catalysts. Under the reaction conditions of 463 K, 0.1 Mpa, NH₃/NO = 1, GHSV = 35,000 h⁻¹, and V₂O₅ loading of 2.35 wt%, the outer diameter of CNTs of 60–100 nm, the NO conversion was 92%.     

Low-temperature SCR of NO with NH3 over AC/C supported manganese-based monolithic catalysts

Metal oxide/active carbon/ceramic (MO_x/AC/C) monolithic catalysts were prepared by impregnation method for selective catalytic reduction (SCR) of NO_x with NH₃ at low-temperature, and they also had been characterized by elemental analysis, N₂-BET, XRD, SEM and NO-TPD. The adsorption capability of the monolithic catalyst was greatly enhanced due to the attached active carbon. An ultrasonic treatment was used to improve the impregnation process, and which can increase their catalytic activities. More than 90% NO_x conversion could be achieved over the Mn-based monolithic catalysts at low-temperature, and which could be improved further by doping Ce, from 30% to 78% at 100 °C. Mn–Fe–Ce and Mn–V–Ce monolithic catalysts had better tolerance to SO₂ than Mn or Mn–Ce monolithic catalysts.     

Influence of NH3 and NO oxidation on the SCR reaction mechanism on copper/nickel and vanadium oxide catalysts supported on alumina and titania

The influence of ammonia and nitric oxide oxidation on the selective catalytic reduction (SCR) of NO by ammonia with copper/nickel and vanadium oxide catalysts, supported on titania or alumina have been investigated, paying special attention to N₂O formation. In the SCR reaction, the VTi catalyst had a higher activity than VAl at low temperatures, while the CuNiAl catalyst had a higher activity than CuNiTi. A linear relationship between the reaction rate of ammonia oxidation and the initial reduction temperature of the catalysts obtained by H₂-TPR showed that the formation rate of NH species in copper/nickel catalysts would be higher than in vanadia catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that copper/nickel catalysts presented ammonia coordinated on Lewis acid sites, whereas ammonium ion adsorbed on Brønsted acid sites dominated on vanadia catalysts. The NO oxidation experiments revealed that copper/nickel catalysts had an increase of the NO₂ and N₂O concentrations with the temperature. NO could be adsorbed on copper/nickel catalysts and the NO₂ intermediate species could play an important role in the reaction mechanism. It was suggested that the presence of adsorbed NO₂ species could be related to the N₂O formation.     

SO2及水蒸汽对新型钒氧化物脱氮催化剂活性的影响

以TiO₂/Al₂O₃/堇青石蜂窝陶瓷为载体、V₂O₅-MoO₃-WO₃为活性组分，采用溶胶-凝胶法和浸渍法制备了用于氨法选择性催化还原烟气中NO的新型催化剂，考察了SO₂和水蒸汽对其脱氮活性的抑制作用。结果表明，SO₂和水蒸汽对其活性抑制不明显，催化剂在最佳温度仍然能保持90%的脱氮率。运用红外表征手段对活性抑制后的催化剂表面进行研究，发现有微量的硫酸盐生成。     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Reactivity of titanosilicates-supported catalysts for the selective catalytic reduction of NO with NH3

The zeolites with MEL structure were synthesized via the hydrothermal method and the zeolites-supported catalysts, such as Cu²⁺, Ga³⁺, Co³⁺, Ce²⁺ and VO²⁺/zeolites, were prepared by the incipient wetness impregnation. The structures of the synthesized zeolites were characterized by techniques of XRD, FT-IR, SIMS, ²⁹Si and ²⁷Al MAS NMR. The selective catalytic reduction (SCR) of NO by ammonia was carried out with a glass reactor under a downstream flow. The synthesized TS-2 showed no significant DeNO_x activity, instead of catalyzing the ammonia oxidation at a high temperature. Furthermore, the catalytic activity of TS2 zeolite can be effectively modified and tuned up through incorporating second metal ion such as Fe³⁺, Co³⁺, and Al³⁺ into the framework (i.e., [Fe,Ti]Z11, [Co,Ti]Z11, and [Al,Ti]Z11). Among the synthesized bimetallosilicates, the [Fe,Ti]Z11 zeolite is the most active catalyst for the SCR DeNO_x with ammonia; the NO conversion and the N₂ yield reach around 80%. In addition, impregnating the metal ions on TS2 or bimetallosilicates is also a very effective way to improve the SCR DeNO_x activity. Ga³⁺/[Fe40,Ti40]Z11 and Co³⁺/[Fe40,Ti40]Z11 are the most active catalysts and show a potential for the practical applications.     

Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

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.     

添加硅溶胶对平板式脱硝催化剂性能的影响

采用硅溶胶作为粘结剂制备VMo/Ti平板式脱硝催化剂,考察了硅溶胶的添加对催化剂物化性能和脱硝性能的影响。结果表明,硅溶胶的添加可以提升催化剂的耐磨性能,增加催化剂的比表面积,促进活性组分的分散。然而硅溶胶同时也降低了催化剂的还原性能和酸性性能,对催化剂的脱硝性能有不利影响。相比之下,VMo/Si(5)-Ti是较为合适的工业催化剂配方。     

Development of the efficient TiO2 photocatalyst in photoassisted selective catalytic reduction of NO with NH3

Photoassisted selective catalytic reduction (photo-SCR) of NO with NH₃ in the presence of O₂ takes place at room temperature over TiO₂ photocatalyst. From the results of photo-SCR reaction over various TiO₂, we found that JRC-TIO-11 exhibited the best activity. The reaction activity correlated to the amount of acid sites of TiO₂, but did not depend on the specific surface area and crystal diameter. The mixture of rutile and anatase shows higher activity than any of the corresponding TiO₂ single phase catalyst.     

Catalytic performance of Ag–Al2O3 catalyst for the selective catalytic reduction of NO by higher hydrocarbons

Silver–aluminum mixed oxide catalyst (Ag–Al₂O₃) prepared by the sol–gel method was studied for the selective reduction of NO by various alkanes in the presence of water vapor. As the carbon number of alkanes increases, the de-NO_x activity and water tolerance were markedly increased. In the case of n-octane as a reductant, the presence of water vapor markedly promoted NO reduction. The results of reaction studies and in situ IR experiment showed that the possible reasons for the promoting effect by water vapor are the inhibition of the n-octane oxidation by O₂ and the suppression of the poisoning effect caused by carboxylate and carbonate species. Among various alumina-supported transition metal catalysts, Ag–Al₂O₃ showed the highest activity for SCR by n-octane. Ag–Al₂O₃ showed higher NO conversion to N₂ and selectivity than alumina-supported Pt and Cu-ZSM-5 catalysts for the selective reduction of NO by n-octane and i-octane.     

Characterization and activity of novel copper-containing catalysts for selective catalytic reduction of NO with NH3

Cu/Mg/Al mixed oxides (CuO = 4.0–12.5 wt%), obtained by calcination of hydrotalcite-type (HT) anionic clays, were investigated in the selective catalytic reduction (SCR) of NO by NH₃, either in the absence or presence of oxygen, and their behaviours were compared with that of a CuO-supported catalyst (CuO = 10.0 wt%), prepared by incipient wetness impregnation of a Mg/Al mixed oxide also obtained by calcination of an HT precursor. XRD analysis, UV-visible-NIR diffuse reflectance spectra and temperature-programmed reduction analyses showed the formation, in the mixed oxide catalysts obtained from HT precursors, mainly of octahedrally coordinated Cu²⁺ ions, more strongly stabilized than Cu-containing species in the supported catalyst, although the latter showed a lower percentage of reduction. The presence of well dispersed Cu²⁺ ions improved the catalytic performances, although similar behaviours were observed for all catalysts in the absence of oxygen. On the contrary, when the mixture with excess oxygen was fed, very interesting catalytic performances were obtained for the catalyst richest in copper (CuO = 12.5 wt%). This catalyst exhibited a behaviour comparable to that of a commercial V₂O₅–WO₃TiO₂ catalyst, without any deactivation phenomena after four consecutive cycles and following 8 h of time-on-stream at 653 K. Decreasing the copper content or increasing the calcination time and temperature led to considerably poorer performances and catalytic behaviours similar to that of the CuO-supported catalyst, due to the side-reaction of NH₃ combustion on the free Mg/Al mixed oxide surface.     

TiO2-SiO2 and V2O5/TiO2-SiO2 catalyst: Physico-chemical characteristics and catalytic behavior in selective catalytic reduction of NO by NH3

TiO₂-SiO₂ with various compositions prepared by the coprecipitation method and vanadia loaded on TiO₂-SiO₂ were investigated with respect to their physico-chemical characteristics and catalytic behavior in SCR of NO by NH₃ and in the undesired oxidation of SO₂ to SO₃, using BET, XRD, XPS, NH₃-TPD, acidity measurement by the titration method and activity test. TiO₂-SiO₂, compared with pure TiO₂, exhibits a remarkably stronger acidity, a higher BET surface area, a lower crystallinity of anatase titania and results in allowing a good thermal stability and a higher vanadia dispersion on the support up to high loadings of 15 wt% V₂O₅. The SCR activity and N₂ selectivity are found to be more excellent over vanadia loaded on TiO₂-SiO₂ with 10–20 mol% of SiO₂ than over that on pure TiO₂, and this is considered to be associated with highly dispersed vanadia on the supports and large amounts of NH₃ adsorbed on the catalysts. With increasing SiO₂ content, the remarkable activity decrease in the oxidation of SO₂ to SO₃, favorable for industrial SCR catalysts, was also observed, strongly depending on the existence of vanadium species of the oxidation state close to V⁴⁺ on TiO₂-SiO₂, while V⁵⁺ exists on TiO₂, according to XPS. It is concluded that vanadia loaded on Ti-rich TiO₂-SiO₂ with low SiO₂ content is suitable as SCR catalysts for sulfur-containing exhaust gases due to showing not only the excellent de-NO_x activity but also the low SO₂ oxidation performance.     

Low-temperature SCR of NOx with NH3 over carbon–ceramic cellular monolith-supported manganese oxides

This work describes the development and use of carbon–ceramic cellular monoliths as catalyst supports for the low-temperature selective catalytic reduction (SCR) of NO_x with ammonia. Manganese oxide was selected as catalyst and deposited over the support, which was obtained by coating the cellular ceramics with a polymeric film. The coated material was cured, carbonised and activated prior to impregnation of the active phase. The produced catalysts showed a good NO_x reduction (in the range 34–73%) at 150°C for a space velocity of 4000 h⁻¹. Gasification of the support was negligible at the mentioned conditions.     

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.     

Hydrothermal synthesis of vanadium oxide nanotubes from V2O5 gels

Vanadium oxide nanotubes (VO_x-NT) have been synthesized in high yield by adding hexadecylamine to V₂O₅·nH₂O gels, followed by a hydrothermal treatment (150–180 °C, 2–7 days). Scanning electron microscopy (SEM) and X-ray diffraction analysis have been performed to optimize the temperature and reaction time required for formation of VO_x-NT and the morphology of the nanotubes investigated by transmission electron microscopy (TEM).     

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.     

Enhanced catalytic activity for selective catalytic reduction of NO over titanium nanotube-confined CeO2 catalyst

Titanium nanotubes (TNTs)-confined ceria were for the first time prepared in this paper and used for selective catalytic reduction (SCR) of NO with ammonia. In comparison with the catalysts supported by TiO₂ nanoparticles, the confined ceria showed a superiority in SCR of NO due to the improved redox potential and special adsorption of NH₃, where its NO conversion could exceed 95% at reaction temperature of 270–500 °C, which was much higher than that of TiO₂ nanoparticle supported catalysts.