NOx storage-reduction over Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios

A series of Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios were prepared. The NOx storage capacities of these catalysts were measured by isothermal storage at 350 degreesC. It was found that the NOx storage capacity increased with increasing Mg/Al atomic ratios. The catalytic behaviors of Pt/Mg-Al-O and Pt/MgO were studied with storage-reduction cycles at 400 degreesC. Under oxidizing conditions, NOx concentration in the outlet gas gradually increased with time, which indicated the catalysts could store NOx effectively. After a switch from oxidizing conditions to reducing conditions, NOx desorption peak emerged immediately due to the incomplete reduction of stored NOx, which lowered the total NOx conversion. With increasing Mg/Al atomic ratio in the catalysts, NOx conversion increases. Pt/MgO has the highest NOx conversion because of its best activity in the reduction of NOx by C3H6. It seems that with an increasing amount of MgO in the catalysts, the self-poisoning of Pt-sites by adsorbed species during the reaction of NOx with C3H6 may be inhibited effectively.

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Origin of double dinitrogen release feature during fast switching between lean and rich cycles for NOx storage reduction catalysts

The performance of NOx storage and reduction over 1.5 wt% Pt/20 wt% KNO3/K2Ti8O17 and 1.5 wt% Pt/K2Ti8O17 catalysts has been investigated using combined fast transient kinetic switching and isotopically labelled (NO)-N-15 at 350 degrees C. The evolution of product N-2 has revealed two significant peaks during 60 s lean/1.3 s rich switches. It also found that the presence of CO2 in the feed affects the release of N-2 in the second peak. Regardless of the presence/absence of water in the feed, only one peak of N-2 was observed in the absence of CO2. Gas-phase NH3 was not observed in any of the experiments. However, in the presence of CO2 the results obtained from in situ DRIFTS-MS analysis showed that isocyanate species are formed and stored during the rich cycles, probably from the reaction between NOx and CO, in which CO was formed via the reverse water-gas shift reaction. 

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

A fast transient kinetic study of the effect of H-2 on the selective catalytic reduction of NOx with octane using isotopically labelled (NO)-N-15

The H-2-assisted hydrocarbon selective catalytic reduction (HC-SCR) of NO, was investigated using fast transient kinetic analysis coupled with isotopically labelled (NO)-N-15. This allowed monitoring of the evolution of products and reactants during switches of H-2 in and out of the SCR reaction mix. The results obtained with a time resolution of less than 1 s showed that the effect on the reaction of the removal or addition of H-2 was essentially instantaneous. This is consistent with the view that H-2 has a direct chemical effect on the reaction mechanism rather than a secondary one through the formation of "active" Ag clusters. The effect of H-2 partial pressure was investigated at 245 degrees C, it was found that increasing partial pressure of H-2 resulted in increasing conversion of NO and octane. It was also found that the addition of H-2 at 245 degrees C had different effects on the product distribution depending on its partial pressure. The change of the nitrogen balance over time during switches in and out of hydrogen showed that significant quantities of N-containing species were stored when hydrogen was introduced to the system. The positive nitrogen balance on removal of H-2 from the gas phase showed that these stored species continued to react after removal of hydrogen to form N-2. (c) 2006 Elsevier Inc. All rights reserved.

Regeneration mechanism of a Lean NOx Trap (LNT) catalyst in the presence of NO investigated using isotope labelling techniques

The presence of NO during the regeneration period of a Pt-Ba/Al O Lean NO Trap (LNT) catalyst modifies significantly the evolution of products formed from the reduction of stored nitrates, particularly nitrogen and ammonia. The use of isotope labelling techniques, feeding NO during the storage period and NO during regeneration allows us to propose three different routes for nitrogen formation based on the different masses detected during regeneration, i.e. N (m/e = 28), N N (m/e = 29) and N (m/e = 30). It is proposed that the formation of nitrogen via Route 1 involves the reaction between hydrogen and NO released from the storage component to form NH mainly. Then, ammonia further reacts with NO located downstream to form N . In Route 2, it is postulated that the incoming NO reacts with hydrogen to form NH in the reactor zone where the trap has been already regenerated. This isotopically labelled ammonia travels through the catalyst bed until it reaches the regeneration front where it participates in the reduction of stored nitrates ( NO ) to form N N. The formation of N via Route 3 is believed to occur by the reaction between incoming NO and H . The modification of the hydrogen concentration fed during regeneration affects the relative importance of H or NH as reductants and thus the production of N via Route 1 and N N via Route 2.

NOx storage and reduction over copper-based catalysts. Part 2: Ce0.8M0.2Oδ supports (M = Zr, La, Ce, Pr or Nd)

5% copper catalysts with Ce0.8M0.2Oδ supports (M = Zr, La, Ce, Pr or Nd) have been studied by rapid-scan operando DRIFTS for NOx Storage and Reduction (NSR) with high frequency (30 s) CO, H2 and 50%CO + 50%H2 micropulses. In the absence of reductant pulses, below 200–250 °C NOx was stored on the catalysts as nitrite and nitro groups, and above this temperature nitrates were the main species identified. The thermal stability of the NOx species stored on the catalysts depended on the acid/basic character of the dopant (M more acidic = NOx stored less stable ⇒ Zr4+ < none < Nd3+ < Pr3+ < La3+ ⇐ M more basic = NOx stored more stable). Catalysts regeneration was more efficient with H2 than with CO, and the CO + H2 mixture presented an intermediate behavior, but with smaller differences among the series of catalyst than observed using CO alone. N2 is the main NOx reduction product upon H2 regeneration. The highest NOx removal in NSR experiments performed at 400 °C with CO + H2 pulses was achieved with the catalyst with the most basic dopant (CuO/Ce0.8La0.2Oδ) while the poorest performing catalyst was that with the most acidic dopant (CuO/Ce0.8Zr0.2Oδ). The poor performance of CuO/Ce0.8Zr0.2Oδ in NSR experiments with CO pulses was attributed to its lower oxidation capacity compared to the other catalysts.

Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

Improving detection probabilities for pests in stored grains

BACKGROUND: The presence of insects in stored grains is a significant problem for grain farmers, bulk grain handlers and distributors worldwide. Inspections of bulk grain commodities is essential to detect pests and therefore to reduce the risk of their presence in exported goods. It has been well documented that insect pests cluster in response to factors such as microclimatic conditions within bulk grain. Statistical sampling methodologies for grains, however, have typically considered pests and pathogens to be homogeneously distributed throughout grain commodities. In this paper we demonstrate a sampling methodology that accounts for the heterogeneous distribution of insects in bulk grains. RESULTS: We show that failure to account for the heterogeneous distribution of pests may lead to overestimates of the capacity for a sampling program to detect insects in bulk grains. Our results indicate the importance of the proportion of grain that is infested in addition to the density of pests within the infested grain. We also demonstrate that the probability of detecting pests in bulk grains increases as the number of sub-samples increases, even when the total volume or mass of grain sampled remains constant. CONCLUSION: This study demonstrates the importance of considering an appropriate biological model when developing sampling methodologies for insect pests. Accounting for a heterogeneous distribution of pests leads to a considerable improvement in the detection of pests over traditional sampling models.

Influence of iodine value on combustion and NOx emission characteristics of a DI diesel engine

Biodiesel is a renewable fuel that has been shown to reduce many exhaust emissions, except oxides of nitrogen (NOx), in diesel engine cars. This is of special concern in inner urban areas that are subject to strict environmental regulations, such as EURO norms. Also, the use of pure biodiesel (B100) is inhibited because of its higher NOx emissions compared to petroleum diesel fuel. The aim of this present work is to investigate the effect of the iodine value and cetane number of various biodiesel fuels obtained from different feed stocks on the combustion and NOx emission characteristics of a direct injection (DI) diesel engine. The biodiesel fuels were chosen from various feed stocks such as coconut, palm kernel, mahua (Madhuca indica), pongamia pinnata, jatropha curcas, rice bran, and sesame seed oils. The experimental results show an approximately linear relationship between iodine value and NOx emissions. The biodiesels obtained from coconut and palm kernel showed lower NOx levels than diesel, but other biodiesels showed an increase in NOx. It was observed that the nature of the fatty acids of the biodiesel fuels had a significant influence on the NOx emissions. Also, the cetane numbers of the biodiesel fuels are affected both premixed combustion and the combustion rate, which further affected the amount of NOx formation. It was concluded that NOx emissions are influenced by many parameters of biodiesel fuels, particularly the iodine value and cetane number.

Insect distributions and sampling protocols for stored commodities

Purpose of review: This review provides an overview on the importance of characterising and considering insect distribution infor- mation for designing stored commodity sampling protocols. Findings: Sampling protocols are influenced by a number of factors including government regulations, management practices, new technology and current perceptions of the status of insect pest damage. The spatial distribution of insects in stored commodities influ- ences the efficiency of sampling protocols; these can vary in response to season, treatment and other factors. It is important to use sam- pling designs based on robust statistics suitable for the purpose. Future research: The development of sampling protocols based on flexible, robust statistics allows for accuracy across a range of spatial distributions. Additionally, power can be added to sampling protocols through the integration of external information such as treatment history and climate. Bayesian analysis provides a coherent and well understood means to achieve this.

Geostatistical analysis of adult Rhyzopertha dominica (F.) (Coleoptera: Bostrichidae) in wheat stored at constant temperatures

Insect monitoring and sampling programmes are used in the stored grains industry for the detection and estimation of insect pests. At the low pest densities dictated by economic and commercial requirements, the accuracy of both detection and abundance estimates can be influenced by variations in the spatial structure of pest populations over short distances. Geostatistical analysis of Rhyzopertha dominica populations in 2 dimensions showed that, in both the horizontal and vertical directions and at all temperatures examined, insect numbers were positively correlated over short (0-5cm) distances, and negatively correlated over longer (≥10cm) distances. Analysis in 3 dimensions showed a similar pattern, with positive correlations over short distances and negative correlations at longer distances. At 35°C, insects were located significantly further from the grain surface than at 25 and 30°C. Dispersion metrics showed statistically significant aggregation in all cases. This is the first research using small sample units, high sampling intensities, and a range of temperatures, to show spatial structuring of R. dominica populations over short distances. This research will have significant implications for sampling in the stored grains industry.

Identification of copper species present in Cu-ZSM-5 catalysts for NOx reduction

The structure of Cu-ZSM-5 catalysts that show activity for direct NO decomposition and selective catalytic reduction of NOx by hydrocarbons has been investigated by a multitude of modern surface analysis and spectroscopy techniques including X-ray photoelectron spectroscopy, thermogravimetric analysis, and in situ Fourier transform infrared spectroscopy. A series of four catalysts were prepared by exchange of Na-ZSM-5 with dilute copper acetate, and the copper loading was controlled by variation of the solution pH. Underexchanged catalysts contained isolated Cu2+OH-(H2O) species and as the copper loading was increased Cu2+ ions incorporated into the zeolite lattice appeared. The sites at which the latter two copper species were located were fundamentally different. The Cu2+OH-(H2O) moieties were bound to two lattice oxygen ions and associated with one aluminum framework species. In contrast, the Cu2+ ions were probably bound to four lattice oxygen ions and associated with two framework aluminum ions. Once the Cu-ZSM-5 samples attained high levels of exchange, the development of [Cu(μ-OH)2Cu]n2+OH-(H2O) species along with a small concentration of Cu(OH)2 was observed. On activation in helium to 500°C the Cu2+OH-(H2O) species transformed into Cu2+O- and Cu+ moieties, whereas the Cu2+ ions were apparently unaffected by this treatment (apart from the loss of ligated water molecules). Calcination of the precursors resulted in the formation of Cu2+O2- and a one-dimensional CuO species. Temperature-programmed desorption studies revealed that oxygen was removed from the latter two species at 407 and 575°C, respectively. © 1999 Academic Press.

Uniform Civil Procedure Rules r150 : orders relating to "property" – whether sperm extracted and stored may be characterised as “property”

In Bazley v Wesley Monash IVF Pty Ltd [2010] QSC 118 an order was made under r 250 of the Uniform Civil Procedure Rules 1999 (Qld) (“UCPR”) requiring the respondent to continue to hold and maintain straws of semen belonging to the applicant’s deceased husband. The decision includes a useful analysis of the development of the common law regarding property rights in human bodies and body parts.