Catalytic reduction of N2O by ethylbenzene over novel hydrotalcite-derived Mg–Cr–Fe–O as an alternative route for simultaneous N2O abatement and styrene production

New hydrotalcite-like materials containing magnesium, chromium, and/or iron were synthesized by the coprecipitation method and then thermally transformed into mixed metal oxides. The obtained catalysts were characterized with respect to chemical composition (XRF), structural (XRD, Mössbauer spectroscopy) and textural (BET) properties. The catalytic performance of the hydrotalcite-derived oxides was tested in the N₂O decomposition and the N₂O reduction by ethylbenzene. An influence of N₂O/ethylbenzene molar ratio on the process selectivity was studied. The relationship between catalytic performance and structure of catalysts was discussed.     

A kinetic study of NOx reduction over Pt/SiO2 model catalysts with hydrogen as the reducing agent

Flow reactor experiments and kinetic modeling have been performed in order to study the mechanism and kinetics of NO_x reduction over Pt/SiO₂ catalysts with hydrogen as the reducing agent. The experimental results from NO oxidation and reduction cycles showed that N₂O and NH₃ are formed when NO_x is reduced with H₂. The NH₃ formation depends on the H₂ concentration and the selectivity to NH₃ and N₂O is temperature dependent. A previous model has been used to simulate NO oxidation and a mechanism for NO_x reduction is proposed, which describes the formation/consumption of N₂, H₂O, NO, NO₂, N₂O, NH₃, O₂ and H₂. A good agreement was found between the performed experiments and the model.     

N2O decomposition over the circulating ashes from coal-fired CFB boilers

The catalytic decomposition of N₂O over the circulating ashes from coal-fired circulating fluidized bed (CFB) boilers was investigated with a fixed bed reactor. The associated kinetics was mimicked by four surrogate metal oxides of SiO₂, Al₂O₃, CaO and Fe₃O₄, which were found as the main components of the circulating ashes. The activation energies and collision coefficients for N₂O thermal decomposition over the circulating ashes and surrogates were individually measured. Experimental results showed that different metal oxides play different roles in the catalytic decomposition of N₂O. Among the components, CaO and Fe₃O₄ are very active, while Al₂O₃ and SiO₂ contribute much less to N₂O destruction. A model based on the specific surface-area-weighted kinetic data of individual surrogates was developed to predict the catalytic decomposition of N₂O over circulating ashes. The predictions agreed with the experimental data with a minor discrepancy acceptable in an engineering view. Some discussions on the discrepancy were given. The O₂ effect on the N₂O decomposition over the circulating ashes was experimentally assessed. It was found that the presence of O₂, even with a small amount, would deteriorate the catalytic decomposition of N₂O.     

Effect of support modification by carbon coverage in the dehydrogenation activity of Cu/Al2O3 catalyst

Gamma alumina and carbon covered gamma alumina supported Cu catalysts were prepared and characterized by adsorptive decomposition of N₂O, NH₃ chemisorption and temperature-programmed reduction. The decrease in interaction of copper species with alumina of carbon covered alumina has influence on the conversion and selectivity of the reaction of cyclohexanol to cyclohexanone.     

Ammonia and nitrous oxide emissions from grass and alfalfa mulches

Ammonia (NH₃) and nitrous oxide (N_-2O) emissions were measured in the field for three months from three different herbage mulches and from bare soil, used as a control. The mulches were grass with a low N-content (1.15% N in DM), grass with a high N-content (2.12% N in DM) and alfalfa with a high N-content (4.33% N in DM). NH₃ volatilization was measured using a micrometeorological technique. N_-2O emissions were measured using closed chambers. NH₃ and N_-2O emissions were found to be much higher from the N-rich mulches than from the low-N grass and bare soil, which did not differ significantly. Volatilization losses of NH₃ and N_-2O occurred mainly during the first month after applying the herbage and were highest from wet material shortly after a rain. The extent of NH₃-N losses was difficult to estimate, due to the low frequency of measurements and some problems with the denuder technique, used on the first occasions of measurements. Nevertheless, the results indicate that NH₃-N losses from herbage mulch rich in N can be substantial. Estimated losses of NH₃-N ranged from the equivalent of 17% of the applied N for alfalfa to 39% for high-N grass. These losses not only represent a reduction in the fertilizer value of the mulch, but also contribute appreciably to atmospheric pollution. The estimated loss of N_-2O-N during the measurement period amounted to 1% of the applied N in the N-rich materials, which is equivalent to at least 13 kg N_-2O-N ha^-1 lost from alfalfa and 6 kg ha^-1 lost from high-N grass. These emission values greatly exceed the 0.2 kg N_-2O-N ha^-1 released from bare soil, and thus contribute to greenhouse gas emissions.     

Effect of low-sulfur fuels upon NH3 and N2O emission during operation of commercial three-way catalytic converters

The use of low-sulfur fuel is known to improve the performance of the three-way catalytic converter (TWC). However, in this work we report how low-sulfur operation of commercial TWC also favors formation of N₂O and NH₃ as by products. We found that low-sulfur rich operation above 300 °C increases the production of NH₃, inhibiting the formation of N₂O characteristic of high-sulfur operation. During lean operation, the production of N₂O near the stoichiometric point is not significantly affected by the sulfur level. The large production of N₂O observed during light-off is not affected by SO₂ when the operation is lean, but under rich conditions N₂O is produced up to 575 °C. The increased production of NH₃ and N₂O in TWC as a result of the introduction of low-sulfur gasoline is an area that requires further analysis because of its implication upon public health in large urban settings.     

An investigation into the effect of Cs promotion on the catalytic activity of NiO in the direct decomposition of N2O

A series of Cs promoted NiO catalysts have been prepared and tested for direct decomposition of N₂O. These catalysts are characterized by BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of N₂O (TPD-N₂O) and X-ray photo electron spectroscopy (XPS). The Cs promoted NiO catalysts exhibit higher activity for the decomposition of N₂O compared to bulk NiO. The catalyst with Cs/Ni ratio of 0.1 showed highest activity. The enhancement in catalytic activity of the Cs promoted catalysts is attributed to the change in the electronic properties of NiO. The characterization techniques suggest weakening of Ni–O bond thereby the desorption of oxygen becomes more facile during the reaction. The Cs promoted NiO catalyst is effective at low reaction temperature and also in the presence of oxygen and steam in the feed stream. IICT Communication No: 070523.     

A study of nitrous oxide decomposition over calcium oxide

A study of N₂O decomposition reaction in a fixed bed a reactor over bed of CaO particles has been conducted. Effects of parameters such as concentration of inlet N₂O gas, reacting temperature and content of CO₂/ CO gas present in the reacting materials on the decomposition reaction have been investigated. The results showed that the conversion of N₂O decomposition was accelerated by the increase of reaction temperature, and the existence of CO, while the rate was hindered by the existence of CO₂. Heterogeneous gas solid reaction kinetics was proposed for N₂O decomposition and compared with homogeneous reaction kinetics. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Catalytic Performance and Sulfur Dioxide Resistance of One-Pot Synthesized Fe-MCM-22 in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia (NH3-SCR)—The Effect of Iron Content

The catalytic performance of Fe-catalysts in selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR) strongly depends on the nature of iron sites. Therefore, we aimed to prepare and investigate the catalytic potential of Fe-MCM-22 with various Si/Fe molar ratios in NH₃-SCR. The samples were prepared by the one-pot synthesis method to provide high dispersion of iron and reduce the number of synthesis steps. We have found that the sample with the lowest concentration of Fe exhibited the highest catalytic activity of ca. 100% at 175 °C, due to the abundance of well-dispersed isolated iron species. The decrease of Si/Fe limited the formation of microporous structure and resulted in partial amorphization, formation of iron oxide clusters, and emission of N₂O during the catalytic reaction. However, an optimal concentration of Fe_xO_y oligomers contributed to the decomposition of nitrous oxide within 250–400 °C. Moreover, the acidic character of the catalysts was not a key factor determining the high conversion of NO. Additionally, we conducted NH₃-SCR catalytic tests over the samples after poisoning with sulfur dioxide (SO₂). We observed that SO₂ affected the catalytic performance mainly in the low-temperature region, due to the deposition of thermally unstable ammonium sulfates.     

Kinetic evaluation of mechanistic models for O2 release from ZSM-5-supported [Cu2+ –O–Cu2+] ions by thermal reduction or chemical interaction with impinging N2O molecules

For a series of oxidized Cu-ZSM-5 catalysts which were characterized in the catalytic amounts of the oxygen-bridged Cu²⁺-dimers, [Cu²⁺–O–Cu²⁺], activation energies required for the reduction of the Cu²⁺-dimer species by O₂ release were determined using the temperature-programmed experiments of thermal O₂ desorption (TPD) and N₂O decomposition reaction. The activation energy for the thermal reduction of the Cu²⁺-dimers during the TPD decreased linearly with increasing molar number of the Cu²⁺-dimers available on the ZSM-5, suggesting that the energy barrier of the O₂ formation via a Langmuir-Hinshelwood (LH) mechanism increased in proportion to the distance between the two Cu²⁺-dimers in the nearest neighbor. Activation energies of thermal O₂ release were comparable to the literature-reported binding energies of the differently spaced Cu²⁺-dimers. It was also revealed that the activation energy of O₂ release during the temperature programmed N₂O decomposition reaction over an oxidized catalyst was generally low as compared to that in the TPD, and that the degree of reduction of the Cu²⁺-dimers was much greater in the N₂O decomposition reaction than in the TPD at the same temperatures. These beneficial effects N₂O decomposition on the reduction of the Cu²⁺-dimers were discussed in respect of the removal mechanism of the Cu²⁺-dimer bridged oxygen.     

DRIFTS study of the catalytic N2O reduction by SO2 on FeZSM-5

SO₂ has been recognized as an effective reducing agent for N₂O over iron-containing zeolite catalysts, lowering the operation temperature up to 100 K with respect to the direct N₂O decomposition. This unique behavior contrasts with the common poisoning effect of SO₂ over other active de-N₂O metals (e.g. Co, Cu, Rh, and Ru). The formation of surface sulfates has been generally posed as the main cause for catalyst deactivation by SO₂. Through the use of in situ infrared spectroscopy (DRIFTS), we show that steam-activated FeZSM-5 indeed builds up stable sulfate species during the N₂O + SO₂ reaction. Significant amounts of sulfur were detected in the used catalyst by elemental analysis and X-ray photoelectron spectroscopy. However, the enhanced N₂O conversion is remarkably stable, indicating that the reducing action by SO₂ and the sulfation of the surface are decoupled. The resulting sulfate species are thus spectators in the catalytic process and do not block or alter the structure of the active sites for N₂O reduction and decomposition.     

Catalytic reduction of N2O by H2 over well-characterized Pt surfaces

A 0.65% Pt/SiO₂ catalyst has been prepared using an ion exchange technique and extensively characterized prior to being used for continuous catalytic N₂O reduction by H₂ at very low temperatures, such as 363 K. The supported Pt with a high dispersion of 92% gave no presence of O atoms remaining on an H-covered Pt _s , based on in situ DRIFTS spectra of CO adsorbed on Pt _s after either N₂O decomposition at 363 K or subsequent exposure to H₂ for more than 1 h; thus the residual uptake gravimetrically observed even after the hydrogen titration on an O-covered surface is associated with H₂O produced by introducing H₂ at 363 K onto the oxidized Pt _s . Dissociative N₂O adsorption at 363 K on Pt _s was not inhibited by the H₂O_(ad) on the silica surface but not on Pt _s , as acquired by IR peaks at 3,437 and 1,641 cm⁻¹, in very consistent with the same hydrogen coverage, established via H₂-N₂O titration on a reduced Pt _s , as that revealed upon the titration reaction with a fully wet surface on which all bands and their position in IR spectra for CO are very similar to that obtained after H2 titration on a reduced Pt _s . Based on the characterization using chemisorption and in situ DRIFTS and TPD measurements, the complete loss in the rate of N₂O decomposition at 363 K after a certain on-stream hour, depending significantly on N₂O concentrations used, is due to self-poisoning by the strong chemisorption of O atoms on Pt _s , while the presence of H₂ as a reductant could readily catalyze continuous N₂O reduction at 363 K that is a greatly lower temperature than that reported earlier in the literature.     

The influence of silver on the properties of cryptomelane type manganese oxides in N2O decomposition reaction

The cryptomelane type oxides were prepared by the redox precipitation technique using Mn(CH₃COO)₂ and KMnO₄ precursors. Nitrogen sorption, XRD, TEM and TPD of oxygen studies showed changes of the surface, structural and redox properties of the samples upon silver introduction. Samples were investigated in the N₂O decomposition reaction. Direct introduction of silver to the synthesis mixture caused partial distortion of regular channel-like structure of the oxides, leading to the decrease of Mn–O bonds strength. As results samples showed slightly better catalytic activity at low temperatures, but were less stable at high temperatures. An introduction of silver by the impregnation method caused the decrease of the surface area of the samples, increase of surface oxygen mobility, leading to the small changes of activity.     

Dehydrogenation of propane in the presence of N2O over In2O3―Al2O3 mixed oxide catalysts

Dehydrogenation of propane coupled with N₂O over a series of binary In₂O₃―Al₂O₃ mixed oxides was investigated. In contrast to the poor performance for sole N₂O decomposition, a remarkable synergy was identified between N₂O decomposition and propane dehydrogenation. Among the catalysts tested, the In₂O₃―Al₂O₃ sample containing a 20 mol% In₂O₃ showed the highest activity for propane dehydrogenation in the presence of N₂O. Moreover, stability far superior to those of the conventional iron-based materials was observed, attributable to the moderate surface acidity of the In―Al―O composite. The essential role of N₂O is suggested to generate active oxygen species facilitating propane dehydrogenation.     

Vanadium, niobium and tantalum modified mesoporous molecular sieves as catalysts for propene epoxidation

SBA-3 mesoporous molecular sieves doped with transition metal ions (Fe, V, Nb and Ta) have been applied for selective oxidation of propene towards propylene oxide in the presence of N₂O as an oxidant. The kind and amount of applied modifiers significantly affected the catalytic activity. V/SBA-3 was found to be the most active among the catalyst under study. In spite of relatively high selectivity towards propylene oxide (reaching up to 23%), the main oxidation product was still propionaldehyde. Surprisingly, CO_x was not formed over V, Nb and Ta modified SBA-3 catalysts. Additional modification of V containing samples (V/SBA-3) with iron complexes resulted in the further increase in the catalysts activity for epoxidation reaction. A PO selectivity of about 20% could be achieved at a propylene conversion of 17% over mixed Fe/V/SBA-3 catalytic system.     

Low Activation Energy Pathway for the Catalyzed Reduction of Nitrogen Oxides to N<Subscript>2</Subscript> by Ammonia

A low activation energy pathway for the catalytic reduction of nitrogen oxides to N₂, with reductants other than ammonia, consists of two sets of reaction steps. In the first set, part of the NO _x is reduced to NH₃; in the second set ammonium nitrite, NH₄NO₂ is formed from this NH₃ and NO + NO₂. The NH₄NO₂ thus formed decomposes at ~100 °C to N₂ + H₂O, even on an inert support, whereas ammonium nitrate, NH₄NO₃, which is also formed from NH₃ and NO₂ + O₂, (or HNO₃), decomposes only at 312 °C yielding mainly N₂O. Upon applying Redhead's equations for a first order desorption to the decomposition of ammonium nitrite, an activation energiy of 22.4 is calculated which is consistent with literature data. For the reaction path via ammonium nitrite a consumption ratio of 1/1 for NO and NO₂ is predicted and confirmed experimentally by injecting NO into a mixture of NH₃ + NO₂ flowing over a BaNa/Y catalyst. This leads to a yield increase of one N₂ molecule per added molecule of NO. Little N₂ is produced from NH₃ + NO in the absence of NO₂.     

An acid catalyzed step in the catalytic reduction of NO x to N2

Contact of adsorbed ammonium nitrite, NH₄NO₂, with HCl vapor or a solid acid such as the zeolite HY, significantly lowers the temperature of its decomposition to N₂ + H₂O. Protonated NH₄NO₂ decomposes at room temperature. The decomposition of ammonium nitrite is one of the steps in the catalytic reduction of NO _x with ammonia or other reductants.     

Direct decomposition of nitrous oxide in the presence of oxygen over iridium catalyst supported on alumina

Direct decomposition of nitrous oxide (N₂O) on noble metal catalysts supported on alumina was examined in the presence of oxygen. The iridium catalysts supported on alumina showed higher activities than the other noble metal catalysts. Although the catalyst activity was affected by oxygen formed by N₂O decomposition at lower temperatures, desorption of oxygen proceeded promptly at the temperature , and the catalytic activity was recovered by increasing the reaction temperature from 350 to . Therefore, the Ir/Al₂O₃ catalyst can be used for N₂O decomposition in the presence of oxygen at relatively higher temperatures.     

Catalytic activity of (CaO)1−x(ZnO)x solids for the N2O decomposition: relation with photoluminescence

(CaO)_1–x (ZnO) _x mixed oxides (x=0–1), heated at 1423 K under atmospheric conditions, were checked for their catalytic activity in the N₂O decomposition in the temperature range of 450–650°C. Although the catalytic activity was measured in the dark, it was found to be linearly related with the photoluminescence intensity of the catalysts.