Transient reaction analysis and steady-state kinetic study of selective catalytic reduction of NO and NO + NO2 by NH3 over Fe/ZSM-5

The reaction kinetics of selective catalytic reduction (SCR) by NH₃ on NO (standard SCR) and on NO + NO₂ (fast SCR) over Fe/ZSM-5 were investigated using transient and steady-state analyses. In the standard SCR, the N₂ production rate was transiently promoted in the absence of gaseous NH₃; this enhancement can be attributed to the negative reaction order of NH₃ (between −0.21 and −0.11). The steady-state data for the standard SCR could be fit to a Langmuir–Hinshelwood-type reaction between NO_ad and O_ad to form NO₂. In the fast SCR, however, the promotion behavior in the absence of gaseous NH₃ was not observed and the apparent NH₃ order changed from positive to negative with NH₃ concentration. The steady-state rate analysis combined with elementary reaction modeling suggested that competitive adsorption between NO₂ and NH₃ was occurring due to strong NO₂ adsorption; this must be the main reason for the absence of the promotion effect.     

Catalytic decomposition of N2O and catalytic reduction of N2O and N2O + NO by NH3 in the presence of O2 over Fe-zeolite

The decomposition of N₂O, and the catalytic reduction by NH₃ of N₂O and N₂O + NO, have been studied on Fe-BEA, -ZSM-5 and -FER catalysts. These catalysts were prepared by classical ion exchange and characterized by TPR after various activation treatments. Fe-FER is the most active material in the catalytic decomposition because “oxo-species” reducible at low temperature, appearing upon interaction of Fe^II-zeolite with N₂O (-oxygen), are formed in largest amounts with this material. The decomposition of N₂O is promoted by addition of NH₃, and even more with NH₃ + NO in the case of Fe-FER and -BEA. It is proposed that the NO-promoted reduction of N₂O originated from the fast surface reaction between -oxygen O^* and NO^* to yield NO₂^*, which in turn reacts immediately with NH₃.     

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.     

The selective catalytic reduction of NO by propylene over Pt supported on dealuminated Y zeolite

The reactivity of Pt supported on a stable dealuminated Y zeolite (Pt/DeY) for the Selective Catalytic Reduction of NO by hydrocarbons (HC-SCR) has been investigated with a monolith sample. The results show that the Pt/DeY catalyst has substantial activity for this reaction at temperatures between 200 and 300°C. Furthermore, the presence of water and sulfur dioxide, at levels similar to the ones expected in vehicle exhaust gas, does not significantly affect the performance of the catalyst, which makes it a promising candidate for further commercial development. In the same temperature range, oxygen promotes the rate of the NO reduction by assisting in the activation of the hydrocarbon. NO₂ is also formed under the conditions studied as a result of the oxidation of NO. In the presence of the hydrocarbon however, it is preferentially reacting with the hydrocarbon, and reduces primarily back to NO. High selectivities were observed toward the formation of N₂O, which is a primary product of the hydrocarbon-SCR reaction.     

Selective catalytic reduction of NOx with NH3 over Cu-ZSM-5—The effect of changing the gas composition

The selective catalytic reduction of nitrogen oxides (NO_x) with ammonia over ZSM-5 catalysts was studied with and without water vapor. The activity of H-, Na- and Cu-ZSM-5 was compared and the result showed that the activity was greatly enhanced by the introduction of copper ions. A comparison between Cu-ZSM-5 of different silica to alumina ratios was also performed. The highest NO conversion was observed over the sample with the lowest silica to alumina ratio and the highest copper content. Further studies were performed with the Cu-ZSM-5-27 (silica/alumina = 27) sample to investigate the effect of changes in the feed gas. Oxygen improves the activity at temperatures below 250 °C, but at higher temperatures O₂ decreases the activity. The presence of water enhances the NO reduction, especially at high temperature. It is important to use about equal amounts of nitrogen oxides and ammonia at 175 °C to avoid ammonia slip and a blocking effect, but also to have high enough concentration to reduce the NO_x. At high temperature higher NH₃ concentrations result in additional NO_x reduction since more NH₃ becomes available for the NO reduction. At these higher temperatures ammonia oxidation increases so that there is no ammonia slip. Exposing the catalyst to equimolecular amounts of NO and NO₂ increases the conversion of NO_x, but causes an increased formation of N₂O.     

Transition metal oxides supported on active carbons as low temperature catalysts for the selective catalytic reduction (SCR) of NO with NH3

The selective catalytic reduction of nitric oxide with ammonia was studied using Fe₂O₃, Cr₂O₃ and CuO loaded active carbons as catalysts in the presence and absence of oxygen at reaction temperatures between 100 and 500°C. Active carbons pretreated with concentrated nitric acid showed a higher catalytic activity in SCR than catalysts which were oxidized in air. The ash content (from 0.2 to 7.1 wt.%) of different unloaded active carbons had no effect on the catalytic activity below 300°C in the absence of oxygen. However, in the presence of oxygen an increasing ash content resulted in an increase in activity. Transition-metal oxide loading led to an increase in SCR activity, especially in the absence of oxygen. An increasing transition-metal content from 1 to 10 wt.% improved the activity as well. The presence of oxygen in the reaction mixture enhanced the conversion of nitric oxide especially in the low-temperature range between 100 and 200°C. Activity and selectivity of the respective catalysts were influenced by the type of metal oxide: in the presence of oxygen, catalysts with 10 wt.% Fe were the most active and selective.     

Selective catalytic reduction of nitric oxide with ammonia using MoO3/TiO2: Catalyst structure and activity

A series of titania supported MoO₃ catalysts (0–20 wt.-% MoO₃) were prepared by dry impregnation. The influence of the MoO₃ content on their catalytic performance for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of oxygen, as well as on their textural and structural properties has been studied. The samples were characterized by XRD, XPS, IR, and BET and porosimetry measurements. The coverage of the TiO₂ support by surface polymeric molybdenum species (where molybdenum is octahedrally coordinated) increases with the molybdenum loading. The formation of a layer of these interacting species on top of the titania surface is complete in the range 15–20 wt.-% MoO₃. The formation of crystallites of bulk MoO₃ starts before the completion of this surface layer (at around 10 wt.-% MoO₃) and increases progressively as the molybdenum loading increases from 10 to 20 wt.-% MoO₃. The SCR activity of the MoO₃/TiO₂ catalysts increases as the MoO₃ content increases to 15 wt.-% and then, for a further increase of the molybdenum loading, it slightly decreases. No specific influence of the molybdenum content on the resistance of catalysts towards SO₂ was observed; the same slight deactivation took place, when the SCR activity was measured in the presence of SO₂ in the feed, for all samples. Our results indicate that the octahedrally coordinated polymeric molybdenum surface species are mainly responsible for the exhibited SCR activity of the MoO₃/TiO₂ catalysts.     

The origin of N2O formation in the selective catalytic reduction of NOx by NH3 in O2 rich atmosphere on Cu-faujasite catalysts

The selective catalytic reduction (SCR) of NO_x (NO + NO₂) by NH₃ in O₂ rich atmosphere has been studied on Cu-FAU catalysts with Cu nominal exchange degree from 25 to 195%. NO₂ promotes the NO conversion at NO/NO₂ = 1 and low Cu content. This is in agreement with next-nearest-neighbor (NNN) Cu ions as the most active sites and with N_xO_y adsorbed species formed between NO and NO₂ as a key intermediate. Special attention was paid to the origin of N₂O formation. CuO aggregates form 40–50% of N₂O at ca. 550 K and become inactive for the SCR above 650 K. NNN Cu ions located within the sodalite cages are active for N₂O formation above 600 K. This formation is greatly enhanced when NO₂ is present in the feed, and originated from the interaction between NO (or NO₂) and NH₃. The introduction of selected co-cations, e.g. Ba, reduces very significantly this N₂O formation.     

Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3. An FT-IR study

The adsorption and transformation of ammonia over V₂O₅, V₂O₅/TiO₂, V₂O₅-WO₃/TiO₂ and CuO/TiO₂ systems has been investigated by FT-IR spectroscopy. In all cases ammonia is first coordinated over Lewis acid sites and later undergoes hydrogen abstraction giving rise either to NH₂ amide species or to its dimeric form N₂H₄, hydrazine. Other species, tentatively identified as imide NH, nitroxyl HNO, nitrogen anions N₂⁻ and azide anions N₃⁻ are further observed over CuO/TiO₂. The comparison of the infrared spectra of the species arising from both NH₃ and N₂H₄ adsorbed over CuO/TiO₂ strongly suggest that N₂H₄ is an intermediate in NH₃ oxidation over this active selective catalytic reduction (SCR) and selective catalytic oxidation (SCO) catalysts. This implies that ammonia is activated in the form of NH₂ species for both SCR and SCO, and it can later dimerize. Ammonia protonation to ammonium ion is detected over V₂O₅-based systems, but not over CuO/TiO₂, in spite of the high SCR and SCO activity of this catalyst. Consequently Brönsted acidity is not necessary for the SCR activity.     

The selective catalytic oxidation of NH3 over Fe-ZSM-5

The abatement of NH₃ from waste streams has become an important environmental issue. Selective catalytic oxidation (SCO) of NH₃ to N₂ has emerged as a potential technology for taking care of NH₃ slips and NH₃ in waste streams. In this work, we describe the catalytic activity of Fe-zeolite catalysts prepared by incipient wetness technique, ion exchange and hydrothermal synthesis in the SCO of NH₃ to N₂ using a fixed bed flow reactor. Selective catalytic oxidation was carried out at 573–723 K and 10⁵ Pa with gas hourly space velocities (GHSV) between 24 000 and 240 000 h⁻¹. Results obtained showed that Fe-ZSM-5 catalysts prepared by incipient wetness technique were active for NH₃ conversion (77–100%) and selectivity to N₂ (65–100%). Fe-ASA and Fe-Beta showed good catalytic activity and selectivity, but their activity and selectivity were less than that of Fe-ZSM-5. The effects of water vapour, Fe loading, and activation method on the performance of these catalysts was also investigated.     

On the mechanism of selective catalytic reduction of NO by propylene over Cu-Al-MCM-41

The selective catalytic reduction of NO by propene in the presence of excess oxygen over Cu-Al-MCM-41 catalyst has been studied by a number of catalytic techniques to characterize the structural, chemisorptive and reactive properties. The characterization using XRD and NMR revealed that the structure of Cu-Al-MCM-41 remained unchanged after the reaction. The active sites related to the reduction of NO and the reaction mechanism were explored based on the data of H₂ temperature programmed reduction (TPR), NO temperature programmed desorption (TPD), X-ray spectrometry (XPS) and in situ FT-IR. The results showed that a redox of Cu ions in Cu-Al-MCM-41 between monovalent and divalent states happened during the selective catalytic reduction of NO, and the reduction seemed to proceed via the intermediate of organic nitro compounds produced by the reaction of propylene adspecies and NO₂. In addition, the presence of oxygen is essential to the formation of NO₂ intermediate and to the cycle of active center between Cu²⁺ and Cu⁺. However, it also caused the deep oxidation of propylene, leading to the depletion in reducing agent at higher temperature.     

Deactivation of a Fe-ZSM-5 catalyst during the selective catalytic reduction of NO by n-decane: An operando DRIFT study

The selective catalytic reduction (SCR) of NO by n-decane was investigated on a Fe-ZSM-5 prepared by the FeCl₃ sublimation method. NO conversion profiles versus temperature were followed in both temperature programmed surface reaction (TPSR, 10 °C min⁻¹) and steady state experiments. A higher NO conversion with a maximum of ca. 80% at 400 °C is observed in the course of the TPSR tests. This phenomenon has been attributed to strong adsorption of n-decane which protects the active sites against the poisoning. Indeed, in steady state experiments at 390 °C the strong decrease of activity as a function of time on stream is due to the polymerisation of conjugated nitriles. This study indicates that long chain alkanes are not the most adequate reductants of NO for high temperature SCR applications. Moreover, due to an easier polymerization of conjugated nitriles on iron zeolites (stronger Fe Lewis sites), this type of catalyst seems less attractive than Cu-zeolite catalysts for the SCR of NO by hydrocarbons in this respect.     

Formation of active sites on Ir/WO3–SiO2 for selective catalytic reduction of NO by CO

Pretreatment conditions for the activation of Ir/WO₃–SiO₂ for the selective catalytic reduction of NO by CO in the presence of excess O₂ were studied. Sequential treatment involving calcination in the presence of O₂ and H₂O followed by reduction and then re-oxidation under mild conditions was found to effectively activate Ir/WO₃–SiO₂. Temperature-programmed desorption during calcination, X-ray diffraction, and temperature-programmed reduction by H₂ revealed that calcination was necessary for oxidative removal of the NH₃ ligands from the iridium precursor, that reduction produced metallic iridium and partially reduced tungsten oxide, and that re-oxidation produced tungsten oxide with low reducibility. Transmission electron microscopy revealed that Ir was supported on finely dispersed tungsten oxide and that the iridium particle size after the sequential activation was 1–1.5 nm.     

Investigation of the selective catalytic reduction of NO by NH3 on Fe-ZSM5 monolith catalysts

Photocatalytic nitric oxide (NO) decomposition and reduction reactions, using carbon monoxide (CO) as a reducing gas, have been investigated over Degussa P25 titanium dioxide photocatalysts, using a continuous flow reactor. The effects of thermal pretreatment temperature and reaction gas composition on the activity and selectivity of the decomposition and reduction reactions have been evaluated. Prepared materials were characterised by X-ray diffraction (XRD), N₂ physisorption, transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) and findings from these techniques were used to explain the observed photocatalytic properties. XRD and TEM results indicated that for the pretreatment temperatures used (70, 120, 200, 450 and 600 °C) there was no appreciable change in the phase composition and the original composition of ca. 77 vol.% anatase and 23 vol.% rutile was maintained even after treatment at 600 °C. It was found that the photocatalytic activity for both the decomposition and reduction reactions decreased with increasing pretreatment temperature. This was attributed to the removal of surface hydroxyl species that act as active sites for reaction. For the decomposition reactions the only products observed were nitrogen and nitrous oxide and the selectivity for nitrogen formation remained constant (ca. 23%) regardless of the pretreatment temperature. The presence of CO in the reaction gas had a dramatic effect on the selectivity of the reactions with nitrogen selectivities as high as 65% being observed. It was found that as the CO/NO ratio increased the selectivity for nitrogen formation increased.     

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.     

Deactivation by SO2 of MnOx/Al2O3 catalysts used for the selective catalytic reduction of NO with NH3 at low temperatures

Low loaded alumina supported manganese oxides exhibit a high activity and selectivity for the selective catalytic reduction (SCR) of NO in the temperature range 383–623 K. The impact of low concentrations of SO₂ on the activity of these catalysts has been investigated. Upon SO₂ addition to the flue gas, the catalysts lose their high initial activity in a few hours due to stoichiometric SO₂ uptake. Analysis of the deactivated samples by mercury porosimetry, FTIR, TPR and TPD shows that the deactivation is not due to the formation of (bulk or surface) Al₂(SO₄)₃ or deposition of ammonium sulphates. Comparison of the results with unsupported Mn₂O₃ and MnO₂ provides evidence that formation of surface MnSO₄ is the main deactivation route. This process is independent of the oxidation state of the manganese and the presence of oxygen in the gas stream. The formed sulphates decompose at 1020 K and are reduced by H₂ at temperatures above 810 K. This means that regeneration of the catalysts is not very feasible. The results restrict practical application of these catalysts to sulphur free conditions.     

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.     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Selective catalytic reduction of nitric oxide with ammonia at low temperatures

Selective catalytic reduction of nitric oxide with ammonia in synthetic low temperature flue gases has been investigated on a commercially available precious metal catalyst, NO_xCAT 920 LT^TM. It has been found that this catalyst is capable of achieving up to 90% conversion at temperatures below 300°C and low space velocities (12 000 h⁻¹), even in the presence of 20 ppm sulfur dioxide. The ideal ammonia concentration to reduce slip and achieve maximum conversion seems to be a stoichiometric match between ammonia concentration and nitric oxide concentration. A dual site model is proposed to explain the selectivity dependence on the presence of water vapor or sulfur dioxide.