NOx storage-reduction characteristics of Ba-based lean NOx trap catalysts subjected to simulated road aging

In order to study the effect of washcoat composition on lean NOx trap (LNT) aging characteristics, fully formulated monolithic LNT catalysts containing varying amounts of La-stabilized CeO2 (5 wt% La2O3) or CeO2-ZrO2 (Ce:Zr = 70:30) were subjected to accelerated aging on a bench reactor. Subsequent catalyst evaluation revealed that aging resulted in deterioration of the NOx storage, NOx release and NOx reduction functions, whereas the observation of lean phase NO2 slip for all of the aged catalysts indicated that LNT performance was not limited by the kinetics of NO oxidation. After aging, all of the catalysts showed increased selectivity to NH3 in the temperature range 250–450 °C. TEM, H2 chemisorption, XPS and elemental analysis data revealed two main changes which can explain the degradation in LNT performance. First, residual sulfur in the catalysts, present as BaSO4, decreased catalyst NOx storage capacity. Second, sintering of the precious metals in the washcoat was observed, which can be expected to decrease the rate of NOx reduction. Additionally, sintering is hypothesized to result in segregation of the precious metal and Ba phases, resulting in less efficient NOx spillover from Pt to Ba during NOx adsorption, as well as decreased rates of reductant spillover from Pt to Ba and reverse NOx spillover during catalyst regeneration. Spectacular improvement in LNT durability was observed for catalysts containing CeO2 or CeO2-ZrO2 relative to their non-ceria containing analog. This was attributed to (i) the ability of ceria to participate in NOx storage/reduction as a supplement to the main Ba NOx storage component; (ii) the fact that Pt and CeO2(-ZrO2) are not subject to phase segregation; and (iii) the ability of ceria to trap sulfur, resulting in decreased sulfur accumulation on the Ba component.

The Effect of Nutrient-Rich Effluents from Shrimp Farming on Mangrove Soil Carbon Storage and Geochemistry Under Semi-Arid Climate Conditions in Northern Brazil

A semi-arid mangrove estuary system in the northeast Brazilian coast (Ceará state) was selected for this study to (i) evaluate the impact of shrimp farm nutrient-rich wastewater effluents on the soil geochemistry and organic carbon (OC) storage and (ii) estimate the total amount of OC stored in mangrove soils (0–40 cm). Wastewater-affected mangrove forests were referred to as WAM and undisturbed areas as Non-WAM. Redox conditions and OC content were statistically correlated (P < 0.05) with seasonality and type of land use (WAM vs. Non-WAM). Eh values were from anoxic to oxic conditions in the wet season (from − 5 to 68 mV in WAM and from < 40 to > 400 mV in Non-WAM soils) and significantly higher (from 66 to 411 mV) in the dry season (P < 0.01). OC contents (0–40 cm soil depth) were significantly higher (P < 0.01) in the wet season than the dry season, and higher in Non-WAM soils than in WAM soils (values of 8.1 and 6.7 kg m− 2 in the wet and dry seasons, respectively, for Non-WAM, and values of 3.8 and 2.9 kg m− 2 in the wet and dry seasons, respectively, for WAM soils; P < 0.01). Iron partitioning was significantly dependent (P < 0.05) on type of land use, with a smaller degree of pyritization and lower Fe-pyrite presence in WAM soils compared to Non-WAM soils. Basal respiration of soil sediments was significantly influenced (P < 0.01) by type of land use with highest CO2 flux rates measured in the WAM soils (mean values of 0.20 mg CO2 h− 1–g− 1 C vs. 0.04 mg CO2 h− 1–g− 1 C). The OC storage reduction in WAM soils was potentially caused (i) by an increase in microbial activity induced by loading of nutrient-rich effluents and (ii) by an increase of strong electron acceptors [e.g., NO3−] that promote a decrease in pyrite concentration and hence a reduction in soil OC burial. The current estimated OC stored in mangrove soils (0–40 cm) in the state of Ceará is approximately 1 million t.

Sviluppi di catalizzatori per l'abbattimento di NOx in presenza di ossigeno

Il traffico veicolare è la principale fonte antropogenica di NOx, idrocarburi (HC) e CO e, dato che la sostituzione dei motori a combustione interna con sistemi alternativi appare ancora lontana nel tempo, lo sviluppo di sistemi in grado di limitare al massimo le emissioni di questi mezzi di trasporto riveste un’importanza fondamentale. Sfortunatamente non esiste un rapporto ottimale aria/combustibile che permetta di avere basse emissioni, mentre la massima potenza ottenibile dal motore corrisponde alle condizioni di elevata formazione di CO e HC. Gli attuali sistemi di abbattimento permettono il controllo delle emissioni da sorgenti mobili tramite una centralina che collega il sistema di iniezione del motore e la concentrazione di ossigeno del sistema catalitico (posto nella marmitta) in modo da controllare il rapporto aria/combustibile (Fig. 1). Le marmitte catalitiche per motori a benzina utilizzano catalizzatori “three way” a base di Pt/Rh supportati su ossidi (allumina, zirconia e ceria), che, dovendo operare con un rapporto quasi stechiometrico combustibile/comburente, comportano una minore efficienza del motore e consumi maggiori del 20-30% rispetto alla combustione in eccesso di ossigeno. Inoltre, questa tecnologia non può essere utilizzata nei motori diesel, che lavorano in eccesso di ossigeno ed utilizzano carburanti con un tenore di zolfo relativamente elevato. In questi ultimi anni è cresciuto l’interesse per il controllo delle emissioni di NOx da fonti veicolari, con particolare attenzione alla riduzione catalitica in presenza di un eccesso di ossigeno, cioè in condizioni di combustione magra. Uno sviluppo recente è rappresentato dai catalizzatori tipo “Toyota” che sono basati sul concetto di accumulo e riduzione (storage/reduction), nei quali l’NO viene ossidato ed accumulato sul catalizzatore come nitrato in condizioni di eccesso di ossigeno. Modificando poi per brevi periodi di tempo le condizioni di alimentazione da ossidanti (aria/combustibile > 14,7 p/p) a riducenti (aria/combustibile < 14,7 p/p) il nitrato immagazzinato viene ridotto a N2 e H2O. Questi catalizzatori sono però molto sensibili alla presenza di zolfo e non possono essere utilizzati con i carburanti diesel attualmente in commercio. Obiettivo di questo lavoro di tesi è stato quello di ottimizzare e migliorare la comprensione del meccanismo di reazione dei catalizzatori “storage-reduction” per l’abbattimento degli NOx nelle emissioni di autoveicoli in presenza di un eccesso di ossigeno. In particolare lo studio è stato focalizzato dapprima sulle proprietà del Pt, fase attiva nei processi di storage-reduction, in funzione del tipo di precursore e sulle proprietà e composizione della fase di accumulo (Ba, Mg ed una loro miscela equimolare) e del supporto (γ-Al2O3 o Mg(Al)O). Lo studio è stato inizialmente focalizzato sulle proprietà dei precursori del Pt, fase attiva nei processi di storage-reduction, sulla composizione della fase di accumulo (Ba, Mg ed una loro miscela equimolare) e del supporto (γ-Al2O3 o Mg(Al)O). E’ stata effettuata una dettagliata caratterizzazione chimico-fisica dei materiali preparati tramite analisi a raggi X (XRD), area superficiale, porosimetria, analisi di dispersione metallica, analisi in riduzione e/o ossidazione in programmata di temperatura (TPR-O), che ha permesso una migliore comprensione delle proprietà dei catalizzatori. Vista la complessità delle miscele gassose reali, sono state utilizzate, nelle prove catalitiche di laboratorio, alcune miscele più semplici, che tuttavia potessero rappresentare in maniera significativa le condizioni reali di esercizio. Il comportamento dei catalizzatori è stato studiato utilizzando differenti miscele sintetiche, con composizioni che permettessero di comprendere meglio il meccanismo. L’intervallo di temperatura in cui si è operato è compreso tra 200-450°C. Al fine di migliorare i catalizzatori, per aumentarne la resistenza alla disattivazione da zolfo, sono state effettuate prove alimentando in continuo SO2 per verificare la resistenza alla disattivazione in funzione della composizione del catalizzatore. I principali risultati conseguiti possono essere così riassunti: A. Caratteristiche Fisiche. Dall’analisi XRD si osserva che l’impregnazione con Pt(NH3)2(NO2)2 o con la sospensione nanoparticellare in DEG, non modifica le proprietà chimico-fisiche del supporto, con l’eccezione del campione con sospensione nanoparticellare impregnata su ossido misto per il quale si è osservata sia la segregazione del Pt, sia la presenza di composti carboniosi sulla superficie. Viceversa l’impregnazione con Ba porta ad una significativa diminuzione dell’area superficiale e della porosità. B. Caratteristiche Chimiche. L’analisi di dispersione metallica, tramite il chemiassorbimento di H2, mostra per i catalizzatori impregnati con Pt nanoparticellare, una bassa dispersione metallica e di conseguenza elevate dimensioni delle particelle di Pt. I campioni impregnati con Pt(NH3)2(NO2)2 presentano una migliore dispersione. Infine dalle analisi TPR-O si è osservato che: Maggiore è la dispersione del metallo nobile maggiore è la sua interazione con il supporto, L’aumento della temperatura di riduzione del PtOx è proporzionale alla quantità dei metalli alcalino terrosi, C. Precursore Metallo Nobile. Nelle prove di attività catalitica, con cicli ossidanti e riducenti continui in presenza ed in assenza di CO2, i catalizzatori con Pt nanoparticellare mostrano una minore attività catalitica, specie in presenza di un competitore come la CO2. Al contrario i catalizzatori ottenuti per impregnazione con la soluzione acquosa di Pt(NH3)2(NO2)2 presentano un’ottima attività catalitica, stabile nel tempo, e sono meno influenzabili dalla presenza di CO2. D. Resistenza all’avvelenamento da SO2. Il catalizzatore di riferimento, 17Ba1Pt/γAl2O3, mostra un effetto di avvelenamento con formazione di solfati più stabili che sul sistema Ba-Mg; difatti il campione non recupera i valori iniziali di attività se non dopo molti cicli di rigenerazione e temperature superiori ai 300°C. Per questi catalizzatori l’avvelenamento da SO2 sembra essere di tipo reversibile, anche se a temperature e condizioni più favorevoli per il 1.5Mg8.5Ba-1Pt/γAl2O3. E. Capacità di Accumulo e Rigenerabilità. Tramite questo tipo di prova è stato possibile ipotizzare e verificare il meccanismo della riduzione. I catalizzatori ottenuti per impregnazione con la soluzione acquosa di Pt(NH3)2(NO2)2 hanno mostrato un’elevata capacità di accumulo. Questa è maggiore per il campione bimetallico (Ba-Mg) a T < 300°C, mentre per il riferimento è maggiore per T > 300°C. Per ambedue i catalizzatori è evidente la formazione di ammoniaca, che potrebbe essere utilizzata come un indice che la riduzione dei nitrati accumulati è arrivata al termine e che il tempo ottimale per la riduzione è stato raggiunto o superato. Per evitare la formazione di NH3, sul catalizzatore di riferimento, è stata variata la concentrazione del riducente e la temperatura in modo da permettere alle specie adsorbite sulla superficie e nel bulk di poter raggiungere il Pt prima che l’ambiente diventi troppo riducente e quindi meno selettivo. La presenza di CO2 riduce fortemente la formazione di NH3; probabilmente perché la CO2, occupando i siti degli elementi alcalino-terrosi lontani dal Pt, impedisce ai nitriti/nitrati o all’H2 attivato di percorrere “elevate” distanze prima di reagire, aumentando così le possibilità di una riduzione più breve e più selettiva. F. Tempo di Riduzione. Si è migliorata la comprensione del ruolo svolto dalla concentrazione dell’agente riducente e dell’effetto della durata della fase riducente. Una durata troppo breve porta, nel lungo periodo, alla saturazione dei siti attivi, un eccesso alla formazione di NH3 Attraverso queste ultime prove è stato possibile formulare un meccanismo di reazione, in particolare della fase riducente. G. Meccanismo di Riduzione. La mobilità dei reagenti, nitriti/nitrati o H2 attivato è un elemento fondamentale nel meccanismo della riduzione. La vicinanza tra i siti di accumulo e quelli redox è determinante per il tipo di prodotti che si possono ottenere. La diminuzione della concentrazione del riducente o l’aumento della temperatura concede maggiore tempo o energia alle specie adsorbite sulla superficie o nel bulk per migrare e reagire prima che l’ambiente diventi troppo riducente e quindi meno selettivo.

The real-time optimisation of DNO owned storage devices on the LV network for peak reduction

Energy storage is a potential alternative to conventional network reinforcementof the low voltage (LV) distribution network to ensure the grid’s infrastructure remainswithin its operating constraints. This paper presents a study on the control of such storagedevices, owned by distribution network operators. A deterministic model predictive control (MPC) controller and a stochastic receding horizon controller (SRHC) are presented, wherethe objective is to achieve the greatest peak reduction in demand, for a given storagedevice specification, taking into account the high level of uncertainty in the prediction of LV demand. The algorithms presented in this paper are compared to a standard set-pointcontroller and bench marked against a control algorithm with a perfect forecast. A specificcase study, using storage on the LV network, is presented, and the results of each algorithmare compared. A comprehensive analysis is then carried out simulating a large number of LV networks of varying numbers of households. The results show that the performance of each algorithm is dependent on the number of aggregated households. However, on a typical aggregation, the novel SRHC algorithm presented in this paper is shown to outperform each of the comparable storage control techniques.

Control methodologies: Peak reduction algorithms for DNO owned storage devices on the Low Voltage network

The Distribution Network Operators (DNOs) role is becoming more difficult as electric vehicles and electric heating penetrate the network, increasing the demand. As a result it becomes harder for the distribution networks infrastructure to remain within its operating constraints. Energy storage is a potential alternative to conventional network reinforcement such as upgrading cables and transformers. The research presented here in this paper shows that due to the volatile nature of the LV network, the control approach used for energy storage has a significant impact on performance. This paper presents and compares control methodologies for energy storage where the objective is to get the greatest possible peak demand reduction across the day from a pre-specified storage device. The results presented show the benefits and detriments of specific types of control on a storage device connected to a single phase of an LV network, using aggregated demand profiles based on real smart meter data from individual homes. The research demonstrates an important relationship between how predictable an aggregation is and the best control methodology required to achieve the objective.

A peak reduction scheduling algorithm for storage devices on the low voltage network

Reinforcing the Low Voltage (LV) distribution network will become essential to ensure it remains within its operating constraints as demand on the network increases. The deployment of energy storage in the distribution network provides an alternative to conventional reinforcement. This paper presents a control methodology for energy storage to reduce peak demand in a distribution network based on day-ahead demand forecasts and historical demand data. The control methodology pre-processes the forecast data prior to a planning phase to build in resilience to the inevitable errors between the forecasted and actual demand. The algorithm uses no real time adjustment so has an economical advantage over traditional storage control algorithms. Results show that peak demand on a single phase of a feeder can be reduced even when there are differences between the forecasted and the actual demand. In particular, results are presented that demonstrate when the algorithm is applied to a large number of single phase demand aggregations that it is possible to identify which of these aggregations are the most suitable candidates for the control methodology.

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.

New Building - Interior - Press Room - Paper storage - 8x11 Reduction [Detroit News]

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Impact Of Chemical Changes On The Sensory Characteristics Of Coffee Beans During Storage.

Sensory changes during the storage of coffee beans occur mainly due to lipid oxidation and are responsible for the loss of commercial value. This work aimed to verify how sensory changes of natural coffee and pulped natural coffee are related to the oxidative processes during 15 months of storage. During this period, changes in the content of free fatty acids (1.4-3.8 mg/g oil), TBARS values (8.8-10.2 nmol MDA/g), and carbonyl groups (2.6-3.5 nmol/mg of protein) occurred. The intensity of rested coffee flavour in the coffee brew increased (2.1-6.7) and 5-caffeoylquinic acid concentration decreased (5.2-4.6g/100g). Losses were also observed in seed viability, colour of the beans and cellular structure. All the results of the chemical analyses are coherent with the oxidative process that occurred in the grains during storage. Therefore, oxidation would be also responsible for the loss of cellular structure, seed viability and sensory changes.

S-nitrosothiols Regulate Nitric Oxide Production And Storage In Plants Through The Nitrogen Assimilation Pathway.

Nitrogen assimilation plays a vital role in plant metabolism. Assimilation of nitrate, the primary source of nitrogen in soil, is linked to the generation of the redox signal nitric oxide (NO). An important mechanism by which NO regulates plant development and stress responses is through S-nitrosylation, that is, covalent attachment of NO to cysteine residues to form S-nitrosothiols (SNO). Despite the importance of nitrogen assimilation and NO signalling, it remains largely unknown how these pathways are interconnected. Here we show that SNO signalling suppresses both nitrate uptake and reduction by transporters and reductases, respectively, to fine tune nitrate homeostasis. Moreover, NO derived from nitrate assimilation suppresses the redox enzyme S-nitrosoglutathione Reductase 1 (GSNOR1) by S-nitrosylation, preventing scavenging of S-nitrosoglutathione, a major cellular bio-reservoir of NO. Hence, our data demonstrates that (S)NO controls its own generation and scavenging by modulating nitrate assimilation and GSNOR1 activity.

A novel mutation in the glycogen synthase 2 gene in a child with glycogen storage disease type 0

Background: Glycogen storage disease type 0 is an autosomal recessive disease presenting in infancy or early childhood and characterized by ketotic hypoglycemia after prolonged fasting and postprandial hyperglycemia and hyperlactatemia. Sixteen different mutations have been identified to date in the gene which encodes hepatic glycogen synthase, resulting in reduction of glycogen storage in the liver. Case Presentation: Biochemical evaluation as well as direct sequencing of exons and exon-intron boundary regions of the GYS2 gene were performed in a patient presenting fasting hypoglycemia and postprandial hyperglycemia and her parents. The patient was found to be compound heterozygous for one previously reported nonsense mutation (c. 736 C>T; R243X) and a novel frameshift mutation (966_967delGA/insC) which introduces a stop codon 21 aminoacids downstream from the site of the mutation that presumably leads to loss of 51% of the COOH-terminal part of the protein. The glycemia and lactatemia of the parents after an oral glucose tolerance test were evaluated to investigate a possible impact of the carrier status on the metabolic profile. The mother, who presented a positive family history of type 2 diabetes, was classified as glucose intolerant and the father, who did not exhibit metabolic changes after the glucose overload, had an antecedent history of hypoglycemia after moderate alcohol ingestion. Conclusion: The current results expand the spectrum of known mutations in GYS2 and suggest that haploinsufficiency could explain metabolic abnormalities in heterozygous carriers in presence of predisposing conditions.

Equivalent Carbon Dioxide Capture and Storage Processes in Offshore Petroleum Production Facilities

The present study approaches the economic and technical evaluation of equivalent carbon dioxide (CO(2) eqv.) capture and storage processes, considered in a proposal case compared to a base case. The base case considers an offshore petroleum production facility, with high CO(2) content (4 vol%) in the composition of the produced gas and both CO(2) and natural gas emissions to the atmosphere, called CO(2) eqv. emissions. The results obtained with this study, by using a Hysys process simulator, showed a CO(2) emission reduction of 65% comparing the proposal case in relation to the base case.

Ethylene action blockade and cold storage affect ripening of `Golden` papaya fruit

The purpose of this work was to evaluate the effects of ethylene action blockade and cold storage on the ripening of `Golden` papaya fruit. Papayas harvested at maturity stage 1 (up to 15% yellow skin) were evaluated. Half of the fruits, whether treated or not treated with 100 nL L(-1) of 1-methylcyclopropene (1-MCP), were stored at 23A degrees C, while the other half were stored at 11A degrees C for 20 days prior to being stored at 23A degrees C. Non-refrigerated fruits receiving 1-MCP application presented a reduction in respiratory activity, ethylene production, skin color development and pectinmethylesterase activity. Even with a gradual increase in ethylene production at 23A degrees C, fruits treated with 1-MCP maintained a high firmness, but presented a loss of green skin color. Cold storage caused a decrease in ethylene production when fruits were transferred to 23A degrees C. The results suggest that pulp softening is more dependent on ethylene than skin color development, and that some processes responsible for loss of firmness do not depend on ethylene.

Whole-body pre-cooling and heat storage during self-paced cycling performance in warm humid conditions

The aim of this study was to establish the effect that pre-cooling the skin without a concomitant reduction in core temperature has on subsequent self-paced cycling performance under warm humid (31 degrees C and 60% relative humidity) conditions. Seven moderately trained males performed a 30 min self-paced cycling trial on two separate occasions. The conditions were counterbalanced as control or whole-body pre-cooling by water immersion so that resting skin temperature was reduced by approximate to 5-6 degrees C. After pre-cooling, mean skin temperature was lower throughout exercise and rectal temperature was lower (P < 0.05) between 15 and 25 min of exercise. Consequently, heat storage increased (P < 0.003) from 84.0 +/- 8.8 W . m(-2) to 153 +/- 13.1 W . m(-2) (mean +/- s((x) over bar)) after pre-cooling, while total body sweat fell from 1.7 +/- 0.1 1 . h(-1) to 1.2 +/- 0.1 1 . h(-1) (P < 0.05). The distance cycled increased from 14.9 +/- 0.8 to 15.8 +/- 0.7 km (P < 0.05) after pre-cooling. The results indicate that skin pre-cooling in the absence of a reduced rectal temperature is effective in reducing thermal strain and increasing the distance cycled in 30 min under warm humid conditions.