Fe2O3/Al2O3 catalysts for the N2O decomposition in the nitric acid industry

Fe₂O₃ catalysts supported on Al₂O₃ were used to remove nitrous oxide from the nitric acid plant simulated process stream (containing O₂, NO and H₂O). Catalysts were prepared by the coprecipitation method and were characterized for their physico-chemical properties by BET, XRD, AFM and TPR analysis. A strong influence of the post-preparation heating conditions on the structural and catalytic properties of the catalysts has been evidenced. Laboratory tests revealed 95% conversion of N₂O at temperature 750 °C and a slight decrease in activity in the presence of H₂O and NO. The catalysts were inert towards decomposition of NO. The pilot-plant reactor and real plant studies (up to 3300 h time-on-stream) confirmed high activity and very good mechanical stability of the catalysts as well as no decomposition of nitric oxide.     

NO – oxygen scavenger or reaction intermediate in the decomposition of N2O?

Nitric oxide and nitrogen dioxide were found during the thermal desorption of surface species left on Fe-ferrierites after the decomposition of nitrous oxide. This demonstrates the formation of surface NOx species during N₂O decomposition. Repeated decomposition and subsequent desorption of surface species confirm the active role of surface NOx species. Addition of NO up to a fraction of 0.1 times the amount of N₂O increased the decomposition of nitrous oxide as well as the amount of surface NOx species. The use of nitrous oxide labeled with ¹⁸O demonstrated that the zeolite oxygens participate in the reaction and that the presence of NO enhances this participation.     

Effect of noble metals in the decomposition of nitrous oxide over Fe-ferrierites

The decomposition of nitrous oxide was studied over Fe-ferrierite, Me-ferrierites and Fe/Me-ferrierites (Me: Pt, Rh and Ru). Flow as well as batch experiments were carried out and showed a synergy between Fe and Me ions. Ions of noble metals in Fe-ferrierite increased the catalytic activity in the sequence Pt < Rh ≅ Ru. Addition of NO substantially decreased the decomposition of N₂O over Rh/ferrierite and Ru/ferrierite, but not over bimetallic ferrierites. NO _x species created during the decomposition of nitrous oxide alone as well as with addition of NO, and employment of nitrous oxide labeled with ¹⁸O allowed us to assume a changing decomposition mechanism in the presence of Me ions in Fe-ferrierites.     

Reduction of NO by CO under oxidizing conditions over Pt and Rh supported on Al2O3–ZrO2 binary oxides

The platinum and rhodium particles supported on Al₂O₃–ZrO₂ binary oxides were prepared by adding the metal precursors to the binary gel. High specific surface areas (220–250 m²/g) and small metallic particle size (∼20 Å) were obtained. In the reduction of NO by CO without oxygen in the reactant flow high levels of N₂O were achieved, whereas in the presence of oxygen the formation of N₂O notably increases. This selectivity behavior was not observed in catalysts prepared by impregnation with the metallic precursors of Al₂O₃–ZrO₂ mixed oxide stabilized after calcination at 500 °C, since in these catalysts the selectivity to N₂O is the higher with or without oxygen. Thus, it is proposed that the metallic impregnation of gels strongly modifies the mechanism by which the NO reduction by CO occurs.     

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.     

Influence of soil physical properties, fertiliser type and moisture tension on N2O and NO emissions from nearly saturated Japanese upland soils

In Japan, upland soils are an important source of nitrous oxide (N₂O) and nitric oxide (NO) gas emissions. This paper reports on an investigation of the effect of soil moisture near saturation on N₂O and NO emission rates from four upland soils in Japan of contrasting texture. The aim was to relate these effects to soil physical properties. Intact cores of each soil type were incubated in the laboratory at different moisture tensions after fertilisation with NH₄-N, NO₃-N or zero N. Emissions of N₂O and NO were measured regularly over a 16–20 day period. At the end of the incubation, soil cores were analysed for physical properties. Moisture and N fertiliser significantly affected rates of emissions of both N₂O and NO with large differences between the soil types. Nitrous oxide emissions were greatest in the finer-textured soils, whereas NO emissions were greater in the coarser-textured soils. Emissions of N₂O increased at higher moisture contents in all soils, but the magnitude of increase was much greater in finer-textured soils. Nitric oxide emissions were only significant in soils fertilised with NH₄-N and were negatively correlated with soil moisture. Analysis of soil properties showed that there was a strong relationship between the magnitude of emissions and soil physical properties. The importance of soil wetness to gas emissions was mainly through its influence on soil air-filled porosity, which itself was related to gas diffusivity. From the results of this research, we can now estimate likely effects of soil texture on emissions through the influence of soil type on soil aeration and soil drainage. This is of particular value in modelling N₂O and NO emissions from soil moisture status and land use inputs.     

Measurement and modeling of nitrous and nitric oxide emissions from a tea field in subtropical central China

Tea fields represent an important source of nitrous oxide (N₂O) and nitric oxide (NO) emissions due to high nitrogen (N) fertilizer applications and very low soil pH. To investigate the temporal characteristics of N₂O and NO emissions, daily emissions were measured over 2½ years period using static closed-chamber/gas chromatograph and chemiluminescent measurement system in a tea field of subtropical central China. Our results revealed that N₂O and NO fluxes showed similar temporal trends, which were generally driven by temporal variations in soil temperature and soil moisture content and were also affected by fertilization events. The measured average annual N₂O and NO emissions were 10.9 and 3.3 kg N ha^?1 year^?1, respectively, highlighting the high N₂O and NO emissions from tea fields. To improve our understanding of N-cycling processes in tea ecosystems, we developed a new nitrogenous gas emission module for the water and nitrogen management model (WNMM, V2) that simulated daily N₂O and NO fluxes, in which the NO was simulated as being emitted from both nitrification and nitrite chemical decomposition. The results demonstrated that the WNMM captured the general temporal dynamics of N₂O (NSE = 0.40; R² = 0.52, RMSE = 0.03 kg N ha^?1 day^?1, P < 0.001) and NO (NSE = 0.41; R² = 0.44, RMSE = 0.01 kg N ha^?1 day^?1, P < 0.001) emissions. According to the simulation, denitrification was identified as the dominant process contributing 76.5% of the total N₂O emissions, while nitrification and nitrite chemical decomposition accounted for 52.3 and 47.7% of the total NO emissions, respectively.     

Effect of NO on the catalytic removal of N2O over FeZSM-5. Friend or foe

Selective catalytic reduction (SCR) of N₂O with C₃H₈ over FeZSM-5 under excess oxygen is strongly inhibited by NO. The assistance of the hydrocarbon in N₂O reduction vanishes at high partial NO pressures, approaching the activity of the N₂O + NO system at molar NO/N₂O ratios of 1.5–2, with N₂O/C₃H₈=1. This effect differs from the NO promotion in direct N₂O decomposition over Fe-zeolite catalysts. The negative effect of NO on the N₂O reduction has a significant impact in the design and operation of catalytic reactors in tail-gases of nitric acid plants and other sources where NO comes along with N₂O.     

Increased emissions of nitric oxide and nitrous oxide following tillage of a perennial pasture

About 40% of the agricultural land in the European Union (EU) is grassland used for animal production. When grassland is tilled, organically bound carbon and nitrogen are released, providing substrates for nitrifying and denitrifying microorganisms. The aim of this study was to examine the immediate effects of tillage of a perennial grassland carried out on different dates, on the emissions of nitric oxide (NO) and nitrous oxide (N₂O), monitored intensively over a 5-day period, in a humid, dairy farming area of northern Spain. Soil was tilled 12 days and 2 days prior to fertiliser application. Tillage, time of tillage, and N fertiliser application affected NO and N₂O emissions. Tillage 12 days before the start of the flux measurements resulted in higher emissions than tillage one day before, the difference being related to differences in soil mineral N and water-filled pore space (WFPS). Emissions of NO peaked at a WFPS of 50–60%, while N₂O fluxes peaked at 70–90% WFPS. Loss of N was greater as N₂O than as NO. The total loss of N as N₂O plus NO ranged from 0.027 kg N ha^–1 in unfertilised plots to 0.56 kg N ha^–1 in the tilled and N fertilised plot. Thereafter emissions decreased rapidly to low values. The results of this study indicate that tillage of perennial grassland may release large amounts of NO and N₂O, the amounts also depending on moisture conditions and addition of N fertiliser. We suggest that in order to reduce such emissions, application of N fertiliser should not immediately follow tillage of perennial grassland, as there is an extra supply of N from mineralisation of organic matter at this time.     

Effects of the depth of NO and N2O productions in soil on their emission rates to the atmosphere: analysis by a simulation model

Many factors are concerned in the changing forms of nitrogen compounds in soil, so it is not easy to make precise models to simulate the concentration profiles of soil nitric oxide (NO) and nitrous oxide (N₂O) and their emission rates under various soil conditions. We prepared a simple mathematical simulation model based on soil concentration profiles of NO and N₂O. The profiles were measured at lysimeters filled with Andosol soil and fertilized with ammonium sulfate at rate of 200 kgNha^-1, incorporating to plow layer (Hirose & Tsuruta, 1996). In this model, diffusion of gases in soil followed Fick's law and the diffusion coefficient was adopted from Sallam et al. (1984). The gas production rate was set up at constant value in the site of gas production, and the gaseous consumption followed Michaelis-Menten kinetics. By changing only the depth of NO and N₂O production in soil in this model, we obtained the following results.(1) When the depth of gas production was set at near the soil surface (NO: 0–10 cm, N₂O: 0-8 cm), the emission rates of both gases corresponded with the results of the lysimeter-measurement.(2) When the depth of gas production was shifted down 10 cm deeper (NO: 10–20 cm, N₂O: 10-18 cm), the gas emission rate of NO decreased to 1.3% of (1), while that of N₂O was almost the same as (1).(3) In the case that the total intensity of produced gases was not changed from (1) or (2), but that the extent of gas productions expanded 3 times wider (NO: 0–30 cm, N₂O: 0–24 cm) than (1) or (2), the emission rates of NO and N₂O became 26% and 95% of (1), respectively.The above results suggest the possibility of mitigating NO emission by setting the site of gaseous production in deeper soil, e.g. by means of deep application of fertilizer.     

Rates and controls of nitrous oxide and nitric oxide emissions following conversion of forest to pasture in Rondônia

Tropical soils are important sources of nitrous oxide (N₂O) and nitric oxide (NO) emissions from the Earths terrestrial ecosystems. Clearing of tropical rainforest for pasture has the potential to alter N₂O and NO emissions from soils by altering moisture, nitrogen supply or other factors that control N oxide production. In this review we report annual rates of N₂O and NO emissions from forest and pastures of different ages in the western Brazilian Amazon state of Rondônia and examine how forest clearing alters the major controls of N oxide production. Forests had annual N₂O emissions of 1.7 to 4.3 kg N ha^-1 y^-1 and annual NO emissions of 1.4 kg N ha^-1 y^-1. Young pastures of 1–3 years old had higher N₂O emissions than the original forest (3.1–5.1 kg N ha^-1 y^-1) but older pastures of 6 years or more had lower emissions (0.1 to 0.4 kg N ha^-1 y^-1). Both soil moisture and indices of soil N cycling were relatively poor predictors of N₂O, NO and combined N₂O + NO emissions. In forest, high N₂O emissions occurred at soil moistures above 30 water-filled pore space, while NO emissions occurred at all measured soil moistures (18–43). In pastures, low N availability led to low N₂O and NO emissions across the entire range of soil moistures. Based on these patterns and results of field fertilization experiments, we concluded that: (1) nitrification was the source of NO from forest soils, (2) denitrification was not a major source of N₂O production from forest soils or was not limited by NO- supply, (3) denitrification was a major source of N₂O production from pasture soils but only when NO₃^- was available, and (4) nitrification was not a major source of 3 NO production in pasture soils. Pulse wettings after prolonged dry periods increased N₂O and NO₃^- emissions for only short periods and not enough to appreciably affect annual emission rates. We project that Basin-wide, the effect of clearing for pasture in the future will be a small reduction in total N₂O emissions if the extensive pastures of the Amazon continue to be managed in a way similar to current practices. In the future, both N₂Oand NO fluxes could increase if uses of pastures change to include greater use of N fertilizers or N-fixing crops. Predicting the consequences of these changes for N oxide production will require an understanding of how the processes of nitrification and denitrification interact with soil type and regional moisture regimes to control N₂O and NO production from these new anthropogenic N sources.     

A mechanistic study of nitrous oxide adsorption and decomposition on zirconia

FT-IR spectroscopy and mass spectrometry have been used to study the adsorption and decomposition of nitrous oxide on zirconia. It was determined that zirconia cations in the 4+ oxidation state are the site for molecular adsorption of N₂O, whereas Zr³⁺ sites are active toward dissociative adsorption of N₂O at temperatures as low as 25°C. Catalytic decomposition of N₂O on ZrO₂ occurs at temperatures above 350°C and follows first-order reaction kinetics. Experiments utilizing isotopic labeling in conjunction with mass spectrometry were done to elucidate the details of the reaction mechanism. Based on the results presented here, a mechanism for N₂O decomposition on ZrO₂ is proposed. This revised version was published online in July 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.     

The catalytic reduction of nitric oxide over supported ruthenium catalysts

The activity of supported ruthenium catalysts for reducing NO to N₂ in an exhaust-like feedstream has been examined in laboratory experiments. The rate and temperature of NO removal is largely dependent on the NO inlet concentration and independent of the concentration of reducing agents in the system. The selectivity for nitrogen formation, however, is dependent on the concentration of the reducing agents CO and H₂ as well as the concentration of NO. No evidence was found for an ammonia intermediate in the conversion of nitric oxide to elemental nitrogen over ruthenium. The high selectivity of ruthenium for the NO to N₂ conversion is explained and compared with the behavior of platinum and palladium catalysts.     

Synthesis of Pd–alumina and Pd–lanthana Suspension for Catalytic Applications by One-step Liquid Flame Spray

Catalytic materials of alumina and lanthana supported nanosized palladium particles (7 wt%) in a water suspension were prepared by Liquid Flame Spray (LFS) method. The particle production rate was 90 g/h, using liquid precursors containing Al(NO₃)₃ · 9H₂O, La(NO₃)₃ · 6H₂O and Pd(NH₃)₄NO₃ in water solution. In the LFS method, a turbulent, high-temperature (T_max ∼ 2,700 °C) H₂–O₂ flame is used. The liquid precursor is atomized into micron sized droplets by high velocity H₂ flow and introduced into the flame where the droplets will evaporate. The evaporated compounds decompose and the reaction product re-condenses into particulate material. Here, the nanosized particles are formed by gas-to-particle conversion and the micron sized particles via liquid-to-solid route. In this study, the produced particulate material was collected by thermophoresis along with condensing water into a suspension (nanoparticles in water) in a one-step process. Thus, the whole suspension was produced from the end products of the flame. According to TEM-EDS analysis, the particulate material contained micron sized porous aluminum oxide or lanthanum oxide carrier particles, coated by nanosized palladium particles (∼2–10 nm). The surfactant (Rhodasurf-La 42) was injected into the suspension just after collection to reduce agglomeration. Catalytic performance of the produced Pd–lanthana containing suspension was tested in laboratory with synthetic gases, in order to use it as a possible raw material for three-way catalyst (TWC). The suspension was used as Pd raw material in TWC washcoat and dispersed onto a metallic honeycomb.     

Effects of deep application of urea on NO and N2O emissions from an Andisol

A modeling study revealed that the depth of nitric oxide (NO) production in soil is crucial for its flux, while that of nitrous oxide (N₂O) is not. To verify this result, laboratory experiments with soil columns classified as Andisol (Hydric Hapludand) were conducted, with changing the depth of urea application, at 0–0.1 or 0.1–0.2 m. All the NO concentration profiles in soil exhibited a sharp peak at each fertilized layer within 5 days of fertilizer application. NO concentration in soil decreased abruptly as the distance from the fertilized layer increased. These findings imply that NO is produced mainly within the fertilized layer, but does not diffuse widely in the soil columns, because of rapid NO uptake within the soil. As a result, the NO flux from soil columns fertilized at 0.1–0.2 m depth over the 48-day study period was reduced to almost the same rate as that of the unfertilized one. The total NO emissions from soil columns unfertilized and fertilized at 0–0.1 and 0.1–0.2 m depth were 0.02, 1.39 (± 0.05) and 0.05 (± 0.03) kg N ha^–1, respectively, suggesting that NO emission derived from N fertilizer could be reduced to 2% by shifting the depth of fertilizer application by 0.1 m. On the other hand, soil N₂O concentration profiles exhibited a gentler peak, because of the lower uptake by soil. N₂O fluxes were affected more by the soil conditions, e.g. soil water content, than the distance between fertilized depth and soil surface. The total N₂O emissions from soil columns unfertilized and fertilized at 0–0.1 and 0.1–0.2 m were 0.02, 0.16 (± 0.03) and 0.25 (± 0.04) kg N ha^–1, respectively.     

N2O and NO emissions from different N sources and under a range of soil water contents

Emissions of nitrous oxide (N₂O) and nitric oxide (NO) have been identified as one of the most important sources of atmospheric pollution from grasslands. Soils are major sources for the production of N₂O and NO, which are by-products or intermediate products of microbial nitrification and denitrification processes. Some studies have tried to evaluate the importance of denitrification or nitrification in the formation of N₂O or NO but there are few that have considered emissions of both gases as affected by a wide range of different factors. In this study, the importance of a number of factors (soil moisture, fertiliser type and temperature) was determined for N₂O and NO emissions. Nitrous oxide and NO evolution in time and the possibility of using the ratio NO:N₂O as an indicator for the processes involved were also explored. Dinitrogen (N₂) and ammonia (NH₃) emissions were estimated and a mass balance for N fluxes was performed. Nitrous oxide and NO were produced by nitrification and denitrification in soils fertilised with and by denitrification in soils fertilised with . Water content in the soil was the most important factor affecting N₂O and NO emissions. Our N₂O and NO data were fitted to quadratic (r=0.8) and negative exponential (r=0.7) equations, respectively. A long lag phase was observed for the N₂O emitted from soils fertilised with (denitrification), which was not observed for the soils fertilised with (nitrification) and was possibly due to a greater inhibiting effect of low temperatures on microbial activity controlling denitrification rather than on nitrification. The use of the NO:N₂O ratio as a possible indicator of denitrification or nitrification in the formation of N₂O and NO was discounted for soils fertilised with . The N mass balance indicated that about 50 kg N ha⁻¹ was immobilised by microorganisms and/or taken up by plant roots, and that most of the losses ocurred in wet soils (WFPS >60%) as N₂ and NH₃ losses (>55%).     

Mechanism of the Reduction by Ammonia of Nitrates Stored onto a Pt–Ba/Al2O3 LNT Catalyst

The mechanism involved in the formation of N₂ and of N₂O during the reduction of nitrates stored onto a Pt–Ba/Al₂O₃ LNT catalyst is investigated using labeled NO and unlabeled ammonia, in the presence and in the absence of NO in the gas phase. The reduction of the stored NO _x species (labeled nitrates) with NH₃ leads to the selective formation of N₂. Based on the isotopic distribution, it appears that N₂ formation occurs primarily through the statistical coupling of N-atoms formed by dissociation of NO and NH₃ at metal Pt sites. When the reduction of the stored nitrates is carried out in the presence of NO in the gas phase, NO is preferentially reduced. This implies that the rate determining step of the reduction of nitrates by ammonia is likely associated with the release of stored NO _x . Negligible amounts of nitrous oxide have been observed during the NH₃-TPSR with adsorbed nitrates, whereas relevant quantities of N₂O have been detected at low temperatures (below 180 °C) in the runs performed in the presence of NO in the gas phase. The data converge to indicate that N₂O formation involves the presence of gaseous NO and this suggests that the formation of nitrous oxide occurs either through the coupling of two adsorbed NO molecules or the recombination of an adsorbed NO molecule with an adsorbed NH _x species.     

Highly active and stable bimetallic Ir/Fe-USY catalysts for direct and NO-assisted N2O decomposition

The current research investigated N₂O decompositions over the catalysts Ir/Fe-USY, Fe-USY and Ir-USY under various conditions, and found that a trace amount of iridium (0.1 wt%) incorporated into Fe-USY significantly enhanced N₂O decomposition activity. The decomposition of N₂O over this catalyst (Ir/Fe-USY-0.1%) was also partly assisted by NO present in the gas mixture, in contrast to the negative effect of NO over noble metal catalysts. Moreover, Ir/Fe-USY-0.1% can decompose more than 90% at 400 °C (i.e. the normal exhaust temperature) under simulated conditions of a typical nitric acid plant, e.g. 5000 ppm N₂O, 5% O₂, 700 ppm NO and 2% H₂O in balance He, and such an activity can be kept for over 110 h under these strict conditions. The excellent properties of bimetallic Ir/Fe-USY-0.1% catalyst are presumably related to the good dispersion of Fe and Ir on the zeolite framework, the formation of framework Al–O–Fe species and the electronic synergy between the Ir and Fe sites. The reaction mechanism for N₂O decomposition has been further discussed on the temperature-programmed desorption profiles of O₂, N₂ and NO₂.