Apparatus for steady-state kinetic measurements of the catalytic reduction of nitric oxide by ammonia on iron oxide

The reduction of nitric oxide with ammonia on an unsupported iron oxide catalyst has been studied in a continuous-flow recycle reactor using simulated flue gas. The responses of the employed reactor system to step and pulse inputs of tracer indicate that the system could be regarded as a continuous stirred tank reactor (CSTR). Preliminary tests were carried out to determine the effect of temperature and particle size on the measured reaction rates. Additional experiments were performed in order to study the influence of oxygen and water concentration on these rates. A gas chromatographic system has been developed to analyze the gas components NO, N₂O, NO₂, NH₃, H₂O, O₂, CO₂ and N₂. In addition, the concentrations of NO and NO₂ were measured with a nondisperse infrared (NDUV/NDIR) analyzer.     

Kinetics of nitrous oxide decomposition over Cu-ZSM-5

The kinetics of nitrous oxide decomposition on an overexchanged Cu-ZSM-5 catalyst were measured using a gradientless reactor. Isothermal oscillations of nitrous oxide and oxygen concentrations can be observed in a broad range of experimental conditions. A transition of the catalytic activity during oscillations is accompanied by a change in the oxygen content of the catalyst and by the formation of traces of nitric oxide. The presence of excess oxygen does not significantly alter the behaviour of the catalyst whereas NO concentrations as low as 10 ppm quench the oscillations in the whole temperature range studied (375 to 450°C), maintaining steady-state operation at maximum catalytic activity. Reaction rates in this ‘ignited’ state are first order with respect to nitrous oxide concentration and not affected by either oxygen or nitric oxide. At temperatures above 400°C, the observed reaction rates are influenced by pore diffusion effects. In the region of intrinsic kinetics, the temperature dependence of the first order rate constant can be described by an activation energy of ca. 100 kJ/mol.     

Comprehensive kinetic characterization of the oxidation and gasification of model and real diesel soot by nitrogen oxides and oxygen under engine exhaust conditions: Measurement, Langmuir-Hinshelwood, and Arrhenius parameters

The reaction kinetics of the oxidation and gasification of four types of model and real diesel soot (light and heavy duty vehicle engine soot, graphite spark discharge soot, hexabenzocoronene) by nitrogen oxides and oxygen have been characterized for a wide range of conditions relevant for modern diesel engine exhaust and continuously regenerating particle trapping or filter systems (0-20% O₂, 0-800 ppm NO₂, 0-250 ppm NO, 0-8% H₂O, 303-773 K, space velocities 1.3 × 10⁴-5 × 10⁵ h⁻¹). Soot oxidation and NO₂ adsorption experiments have been performed in a model catalytic system with temperature controlled flat bed reactors, novel aerosol particle deposition structures, and sensitive multicomponent gas analysis by FTIR spectroscopy. The experimental results have been analyzed and parameterized by means of a simple carbon mass-based pseudo-first-order rate equation, a shrinking core model, oxidant-specific rate coefficients, Langmuir-Hinshelwood formalisms (maximum rate coefficients and effective adsorption equilibrium constants), and Arrhenius equations (effective activation energies and pre-exponential factors), which allow to describe the rate of reaction as a function of carbon mass conversion, oxidant concentrations, and temperature. At temperatures up to 723 K the reaction was driven primarily by NO₂ and enhanced by O₂ and H₂O. Within the technically relevant concentration range the reaction rates were nearly independent of O₂ and H₂O variations, while the NO₂ concentration dependence followed a Langmuir-Hinshelwood mechanism (saturation above ∼200 ppm). Reaction stoichiometry (NO₂ consumption, CO and CO₂ formation) and rate coefficients indicate that the reactions of NO₂ and O₂ with soot proceed in parallel and are additive without significant non-linear interferences. The reactivity of the investigated diesel soot and model substances was positively correlated with their oxygen mass fraction and negatively correlated with their carbon mass fraction.     

The selective non-catalytic reduction of nitric oxide using ammonia at up to 15% oxygen

Selective non-catalytic reduction of nitric oxide (NO) using ammonia was studied with up to 15% (by volume) oxygen at 102 kPa. The experiments were conducted in an electrically heated laminar-flow, quartz reactor using mixtures of N₂, O₂, NO, and CO to simulate exhaust gas. The base case condition included 330 ppmv of NO, 495 ppmv of NH₃, and 15% O₂. At a reactor temperature of 1050 K, 77% of the NO was removed. For a lower oxygen concentration of 1%, the NO removal was as high as 98% at 1100 K. The degraded performance at high oxygen concentrations is attributed to increases in the oxidation reactions. A major result of this work was the quantification of the amount of N₂O in the treated gases. For the base case conditions, 21 ppmv of N₂O was measured for a reactor temperature of 1075 K. Increasing the ratio of NH₃ to NO (by increasing the NH₃ concentration) increased the maximum NO removal and decreased the temperature at which this level of NO removal was achieved. For the higher NH₃ concentrations, however, the N₂O concentration increased to as high as 54 ppmv. The oxidation products of ammonia (in the absence of NO) for these conditions were found to include first N₂O beginning at 900 K and then NO beginning at 1050 K. Comparisons between these experimental results and predictions from the Miller and Bowman (1989) model indicate that further enhancements of the model may be necessary to incorporate the features of high oxygen conditions.     

Synthesis of monodispersed micaceous iron oxide by the oxidation of iron with oxygen under hydrothermal conditions

The oxidation behavior of iron powder with oxygen was investigated in 5–25 m NaOH solutions at 5 MPa of oxygen partial pressure and 130–290°C, where m = mol(kg H₂O)^?1. Monodispersed micaceous iron oxide, α-Fe₂O₃, was synthesized by the oxidation of iron powder with 5 MPa of oxygen in 10–16 m NaOH solutions at 250–270°C. The diameter of micaceous iron oxide greatly changed depending on the reaction conditions such as the temperature, reaction time and concentrations of NaOH and coexisting ions.     

Characteristics of the removal of mercury vapor in coal derived fuel gas over iron oxide sorbents

The characteristics of a novel method for Hg removal using H₂S and sorbents containing iron oxide were studied. Previously, we have suggested that this method is based on the reaction of Hg and H₂S over the sorbents to form HgS. However, the reaction mechanism is not well understood. In this work, the characteristics of the Hg removal were studied to clarify the reaction mechanism. In laboratory made sorbents containing iron oxide were used as the sorbent to remove mercury vapor from simulated coal derived fuel gases having a composition of Hg (4.8 ppb), H₂S (400 ppm), CO (30%), H₂ (20%), H₂O (8%), and N₂ (balance gas). The following results were obtained: (1) The presence of H₂S was indispensable for the removal of Hg from coal derived fuel gas; (2) Hg was removed effectively by the sorbents containing iron oxide in the temperature range of 60-100 °C; (3) The presence of H₂O suppressed the Hg removal activity; (4) The presence of oxygen may play very important role in the Hg removal and; (5) Formation of elemental sulfur was observed upon heating of the used sample.     

Isothermal oscillations in the catalytic decomposition of nitrous oxide over Cu-ZSM-5

The catalytic decomposition of nitrous oxide was studied on a copper-exchanged ZSM-5 catalyst in the temperature range 648–723 K. Using a mixture of 1000 ppm N₂O in nitrogen, isothermal oscillations both in nitrous oxide and oxygen concentrations occurred, accompanied by formation of small amounts of NO. While the addition of excess oxygen did not significantly change frequency and amplitude of the oscillations, even the presence of small amounts of NO immediately quenched the oscillations. The reacting system then remained in the ignited state at high nitrous oxide conversions.     

An overview: Comparative kinetic behaviour of Pt, Rh and Pd in the NO + CO and NO + H2 reactions

This paper reports a comparative kinetic investigation of the overall reduction of NO in the presence of CO or H₂ over supported Pt-, Rh- and Pd-based catalysts. Different activity sequences have been established for the NO+H₂ reaction Pt/Al₂O₃>Pd/Al₂O₃>Rh/Al₂O₃ and for the NO+CO reaction Rh/Al₂O₃>Pd/Al₂O₃> Pt/Al₂O₃. It was found that both reactions differ from the rate determining step usually ascribed to the dissociation of chemisorbed NO molecules. The rate enhancement observed for the NO+H₂ reaction has been mainly related to the involvement of a dissociation step of chemisorbed NO molecules assisted by adjacent chemisorbed H atoms. The calculation of the kinetic and thermodynamic constants from steady-state rate measurements and subsequent comparisons show that Pd and Rh are predominantly covered by chemisorbed NO molecules in our operating conditions which could explain either changes in activity or in selectivity with the lack of ammonia formation on Rh/Al₂O₃ during the NO+H₂ reaction. Interestingly, Pd and Rh exhibit similar selectivity behaviour towards the production of nitrous oxide (N₂O) irrespective of the nature of the reducing agent (CO or H₂). A weak partial pressure dependency of the selectivity is observed which can be related to the predominant formation of N₂ via a reaction between chemisorbed NO molecules and N atoms, while over Pt-based catalysts the associative desorption of two adjacent N atoms would occur simultaneously. Such tendencies are still observed under lean conditions in the presence of an excess of oxygen. However, a detrimental effect is observed on the selectivity with an enhancement of the competitive H₂+O₂ reaction, and on the activity behaviour with a strong oxygen inhibiting effect on the rate of NO conversion, particularly on Rh.     

NO decomposition and reduction on Pt/Al2O3 powder and monolith catalysts using the TAP reactor

A systematic study over Pt/Al₂O₃ powder and monolith catalysts is carried out using temporal analysis of products (TAP) to elucidate the transient kinetics of NO decomposition and NO reduction with H₂. NO pulsing and NO–H₂ pump-probe experiments demonstrate the effect of catalyst temperature, NO–H₂ pulse delay time and H₂/NO ratio on N₂, N₂O and NH₃ selectivity. At lower temperature (150 °C) decomposition of NO is negligible in the absence of H₂, indicating that N–O bond scission is rate limiting. At higher temperature NO decomposition occurs readily on reduced Pt but the rate is inhibited by surface oxygen as reaction occurs. The reduction of NO by a limiting amount of H₂ at lower temperature indicates the reaction of surface NO with H adatoms to form N adatoms, which react with adsorbed NO to form N₂O or recombine to form N₂. In excess H₂, higher temperatures and longer delay times favor the production of N₂. The longer delay enables NO decomposition on reduced Pt with the role of H₂ being a scavenger of surface oxygen. Lower temperatures and shorter delay times are favorable for ammonia production. The sensitive dependence on delay time indicates that the fate of adsorbed NO depends on the concentration of vacant sites for NO bond scission, necessary for N₂ formation, and of surface hydrogen, necessary for hydrogenation to ammonia. A mechanistic-based microkinetic model is proposed that accounts for the experimental observations. The TAP experiments with the monolith catalyst show an improved signal due to the reduction of transport restrictions caused by the powder. The improved signal holds promise for quantitative TAP studies for kinetic parameters estimation and model discrimination.     

Density functional theory studies of mechanistic aspects of the SCR reaction on vanadium oxide catalysts

Density functional theory (DFT) calculations were carried out on a vanadium oxide cluster containing four vanadium atoms to probe the mechanism of the selective catalytic reduction (SCR) of NO with ammonia. The interaction of ammonia with Brønsted acid sites on this V₄-cluster leads to the formation of NH₄ species bonded to two vanadyl (VO) groups, with a bonding energy of −110 kJ/mol. This adsorbed NH₄ species reacts with NO in a series of steps to form an adsorbed NH₂NO species, which subsequently undergoes decomposition to form N₂, H₂O, and a reduced vanadium oxide cluster (V₄H). The latter reaction occurs via a series of hydrogen-transfer steps by a “push–pull” mechanism with adjacent VO and VOH groups on the vanadium oxide cluster. The rate limiting process in this conversion of NO and NH₃ to give N₂, H₂O, and V₄H involves the reaction of an adsorbed NH₃NHO adduct to form NH₂NO species. The transition state of this step may be stabilized through hydrogen bonding with surrounding vanadia and/or titania moieties.     

Kinetics and mechanism of reduction of oxide film on smooth platinum electrodes with hydrogen

The kinetics and mechanism of the reaction of chemisorbed oxide (Pt-O) layer on a smooth Pt electrode with H₂ dissolved in 1 M H₂SO₄ solution were investigated under the open circuit condition.It was found that a monolayer of Pt-O on the electrode surface is reduced first at a slow rate which is of second order in chemisorbed oxygen in the range 1 ≧ θ ≥ 0·65 and then at a rapid rate which is proportional to (1 – nθ)² in the range 0·6 ≥ θ > 0, where θ is the fraction of the surface covered by oxygen. The factor n, which was constant for the electrode oxidized under a given condition, was assumed to be the number of Pt sites deactivated by each one of the chemisorbed oxygen atoms. For the transiently formed oxide, n was estimated to be 1·64. It was also observed that all over the coverage range the reaction rate was proportional to the partial pressure of H₂. The variation in reduction rate with the decrease of the coverage was interpreted in terms of change in reduction mechanism from the chemical reaction to the electrochemical reaction.     

Designing a structured catalyst for selective reduction of O<Subscript>2</Subscript> by hydrogen in the presence of NO

The influence of the promoter (Pd) modifying additives of oxides of rare-earth (La₂O₃, CeO₂) and transition (NiO, CuO) metal oxides on the catalytic activity of Co₃O₄/cordierite in reactions of O₂ and NO reduction by hydrogen was studied. Introducing Pd and rare-earth metal oxides into the composition of cobalt oxide catalyst results in an increase in its activity in H₂ + 1/2O₂ → H₂O, H₂ + NO → 1/2N₂ + H₂O reactions and an increase in selectivity upon oxygen reduction by hydrogen in the presence of nitric oxide, due possibly to a decrease in the strength of oxygen bounds with the surface and the formation of low-temperature forms of oxygen, which is not typical of unpromoted cobalt oxide catalyst. A structured Pd-Co₃O₄-La₂O₃/cordierite catalyst was developed that surpasses the commercial granulated silver-manganese catalyst used in industry to purify the technological gases used in the production of hydroxylamine sulfate of oxygen impurities with reference to activity and selectivity (in the process of oxygen reduction in the presence of nitric oxide), and to thermal stability.     

On the mechanism of the selective catalytic reduction of NO to N2 by H2 over Ru/MgO and Ru/Al2O3 catalysts

Steady-state and transient kinetic experiments were performed in a versatile microreactor flow set-up with magnesia- and alumina-supported ruthenium catalysts in order to elucidate the mechanism of the selective catalytic reduction (SCR) of nitric oxide with hydrogen. Both Ru/MgO and Ru/γ-Al₂O₃ were found to be highly active catalysts converting NO and H₂ into N₂ and H₂O with selectivities close to 100% at full conversion, although Ru-based catalysts are known to be active in the synthesis of NH₃ from N₂ and H₂. Frontal chromatography experiments with NO at room temperature revealed that NO and its dissociation products displace adsorbed atomic hydrogen (H−*) almost completely from hydrogen-precovered Ru surfaces. Obviously, NO and H₂ compete for the same adsorption sites, H−* being the weaker bound adsorbate. Temperature-programmed surface reaction (TPSR) experiments in H₂ subsequent to NO exposure demonstrated that higher heating rates and lower partial pressures of H₂ shift the selectivity from NH₃ to N₂. Therefore, the coverage of H−* is concluded to govern the branching ratio between the rate of associative desorption of N₂ (2N−*→N₂ + 2*) and the rate of hydrogenation of N−* (N−* + 3H–* →NH₃ + 4*). Finally, the steady-state coverages of N- and O-containing adsorbates were derived by interrupting the SCR reaction and hydrogenating the adsorbates off as NH₃ and H₂O. By solving the site balance, the Ru surfaces were found to be essentially N₂ is attributed to the very low coverage of H−* due to site blocking by a N + O coadsorbate layer, favouring the recombination of N−* instead of its hydrogenation to NH₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

Reduction of nitric oxide at a flow-through mercury plated nickel electrode

The electrochemical reduction of nitric oxide at a flow-through mercury-plated nickel gauze electrode in sulphuric acid was investigated. The current efficiencies of hydroxylamine, nitrous oxide and of hydrogen formation were determined. The main experimental results are: 1. The ratio between the NH₂OH and N₂O formation depends on the cd and on the flowrate of the electrolyte through the electrode, but does not depend on the H₂SO₄ concentration in the investigated range from 0.25 to 2.0 M and likewise not on the temperature. 2. The rate of the reduction of nitric oxide to NH₂OH and N₂O increases with increasing cd up to a maximum value, thereafter this rate decreases with increasing cd. 3. The ratio between the current efficiency of the NH₂OH formation and the current efficiency of the N₂O formation increases slowly with increasing cathodic potential.It seems that at low cd (much lower than the cd where the rate of the reduction of NO reaches its maximum) the reduction of NO is affected by both the electrochemical parameters and by the transport of NO to the electrode surface. However, at high current densities the reduction is dominated by mass-transport of NO only. NOH is an intermediate for both the NH₂OH and the N₂O formation.     

Kinetics of dissolution of copper(II) sulphide in aqueous sulphuric acid solutions

The rate of dissolution of synthetic cupric sulphide (CuS) which is the analogue of the naturally occurring sulphide mineral covellite, in sulphuric acid solutions of concentration range 5 × 10^?3 to 3 mole/l over the temperature range 20–65°c at atmospheric pressure was studied. Thermodynamic considerations suggested that the primary reaction taking place during the leaching is: CuS+1/2O₂ + H₂SO₄ → CuSO₄ + S+H₂O. It is proposed that up to an initial sulphuric acid concentration of 1 mole/l, the reaction rate is controlled by the diffusion of H⁺ ions through the sulphur film to the CuS/S interface. For higher sulphuric acid concentrations the oxygen dissolved in the acid decreases and the rate-determining step is believed to be diffusion of dissolved oxygen through the sulphur film to the CuS/S interface. A parabolic model is suggested for the dissolution reaction, and this model is supported by the experimental data. The activation energy for the dissolution reaction was found to be 8000±2000 cal/mole and this was independent of the H⁺ concentration and hence the nature of the diffusing species.     

Selectivity-determining role of C3H8/NO ratio in the reduction of nitric oxide by propane in presence of oxygen over ZSM5 zeolites

The reaction of (NO + C₃H₈ + O₂) can result in selective formation of NO₂ over H-ZSM5, Cu,H-ZSM5, Ag,H-ZSM5, and Li,H-ZSM5 catalysts when the concentrations of NO and O₂ are 0.1 and 9%, SV > 60,000 h⁻¹ (typical for automotive exhausts), and C₃H₈/NO > 1. Despite stoichiometric excess of reductant hydrocarbon below this limit, the in situ formed NO₂ does not react with C₃H₈, thus conversion of NO to N₂ is negligible. NO can be reduced by C₃H₈ selectively to N₂ only when C₃H₈/NO ≧ 1. Contrary to many suggestions the reaction temperature, concentration of oxygen, space velocity, and type of exchange ions have minor influence on the selectivity for N₂. These parameters affect the rates of reactions (NO + ₂), (C₃H₈ + NO_x) and (C₃H₈ + O₂), therefore they also affect the production of N₂ in the HC-SCR process, but only when the ratio of C₃H₈/NO permits. The metal-exchanged zeolites were prepared in situ by solid-state ion exchange from H-ZSM5. Despite the low degree of copper exchange (63%), Cu,H-ZSM5 produces substantially more N₂ than H-ZSM5, Ag,H-ZSM5, or Li,H-ZSM5. However, the selectivity for N₂ is lowest over Cu,H-ZSM5, which also produces considerable NO₂ in the reaction of (NO + C₃H₈ + O₂) even at C₃H₈/NO ≧ 1. Contrary to prior findings, the catalytic activity of Cu,H-ZSM5 for the oxidation of NO by O₂ to NO₂ in absence of hydrocarbon was comparable to that of H-ZSM5 at high space velocities (2.3 l g⁻¹ min⁻¹). By replacing 30 and 40% of the protons of H-ZSM5 by Ag⁺ and Li⁺ ions in Ag,H-ZSM5 and Li,H-ZSM5, respectively, the catalytic activity for this reaction becomes negligible at temperatures ≧100°C. Some mechanistic consequences of these experimental observations are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

The decomposition of nitric oxide on a heated platinum wire

The catalytic rate of decomposition of pure nitric oxide on platinum (2NO → N₂ + O₂) was measured employing the batch, hot-wire technique at wire temperatures in the range 900–1200°C and at total pressures from 400–2260 torr. Chemisorbed oxygen is known to inhibit the rate of this reaction but very little surface oxygen is present at these elevated temperatures and thus an effectively clean platinum surface was realized. Also the experiments were limited to low conversions and thus low oxygen partial pressures (P_O2 → O₂), again minimizing the likelihood of oxygen inhibition. A Rideal—Eley type rate expression: ?r (moles NO reached/cm² . sec) = k₂P²_NO/(1 + K₁P_O2 + K₂P_NO) describes quite well the dependence of the measured rate of the NO partial pressure on P_NO. In contrast the data are not fit well by a Langmuir—Hinshelwood type rate-expression, similar to that above except for a unimolecular term P_NO in the numerator. Owing to the large values of P_NO and low conversions used in the present study with P_O2 → O, the study focused on the kinetics with respect to NO itself. For the above Rideal—Eley mechanism: k₂ ? 4·63 × 10^?4 exp (?8,600/RT) mol/cm² . atm² . sec and K₂ ? 3 · 5 × 10^?2 exp (11,300/RT) atm^?1.     

Iron oxide supported sulfated TiO2 nanotube catalysts for NO reduction with propane

Sulfated TiO₂ nanotubes and a series of iron oxide loaded sulfated TiO₂ nanotubes catalysts with different iron oxide loadings (1 wt%, 3 wt%, 5 wt% and 7 wt%) were prepared and calcined at 400 °C. The physico-chemical properties of the catalysts were studied by using XRD, N₂-physisorption, Raman spectroscopy, SEM-EDX, TEM, XPS, and pyridine adsorption using FTIR and H₂-TPR techniques. It was observed that iron oxide was highly dispersed on the sulfated TiO₂ nanotube support due to its strong interaction. The activity of these catalysts in the catalytic removal of NO with propane was also studied in the temperature range of 300–500 °C. Highest activity (90% NO conversion) was observed with 5 wt% iron oxide supported on sulfated TiO₂ catalyst at 450 °C. Selective catalytic reduction of NO activity of the catalysts was correlated with iron oxide loading, reducibility, and the Brönsted and Lewis acid sites of the catalysts. The catalyst also showed good stability under studied reaction conditions that no deactivation was observed during the 50 h of reaction.     

Absorption of no in aqueous mixed solutions of NaClO2 and NaOH

The absorption of NO in aqueous mixed solutions of NaClO₂ and NaOH was carried out using a semi-batch stirred vessel with a plain gas—liquid interface at 25°C. The rate of absorption was discussed on the basis of chemical absorption theory under the fast-reaction regime. The overall reaction involved was presented by 4NO + 3NaClO₂ + 4NaOH = 4NaNO₃ + 3NaCl + 2H₂O and was found to be second-order with respect to NO and first-order with respect to NaClO₂ in the range of NaClO₂ concentration greater than 0.8 molar. The reaction rate constants evaluated were exponentially decreased with the NaOH concentration and correlated by k = k₀ exp(?3.73 C_EO).     

The positive effect of hydrogen on the reaction of nitric oxide with carbon monoxide over platinum and rhodium catalysts

The effect of adding 330–4930 ppm hydrogen to a reaction mixture of NO and CO (2000 ppm each) over platinum and rhodium catalysts has been investigated at temperatures around 200–250°C. Hydrogen causes large increases in the conversion of NO and, surprisingly, also of CO. Oxygen atoms from the additional NO converted are eventually combined with CO to give CO₂ rather than react with hydrogen to form water. This reaction is described by CO + NO +3/2H₂ CO₂ + NH₃ and accounts for 50–100% of the CO₂ formed with Pt/Al₂O₃ and 20–50% with Rh/Al₂O₃. With the latter catalyst a substantial amount of NO converted produces nitrous oxide. Comparison with a known study of unsupported noble metals suggests that isocyanic acid (HNCO) might be an important intermediate in a reaction system with NO, CO and H₂ present.