Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Risk Factors for Incisional and Organ Space Surgical Site Infections After Liver Resection are Different.

BACKGROUND: Surgical site infection (SSI) is a common cause of major morbidity after liver resection. This study aimed to identify the risk factors for incisional and organ/space SSIs after liver resection. METHODS: Our liver surgery database was retrospectively analyzed for patients treated between January 2009 and November 2012 in a tertiary care Swiss hospital. Univariate and multivariate analyses were conducted on preoperative, intraoperative, and postoperative variables to identify risk factors for incisional and organ/space SSIs. RESULTS: In a total of 226 patients, SSI incidences were 12.8 % (incisional), 4.0 % (organ/space), and 1.8 % (both). Univariate analysis showed that incisional SSIs were associated with high American Society of Anesthesiologists (ASA) scores, preoperative anemia, hypoalbuminemia, low prothrombin time, viral or alcoholic chronic hepatitis, liver cirrhosis, and prolonged operation times. Organ/space SSIs were associated with high rates of red blood cell transfusions, concomitant bowel surgery, and prolonged operation times. Multivariate analysis revealed that risk factors for incisional SSIs were anemia [odds ratio (OR) 2.82], high ASA scores (OR 2.88), presence of hepatitis or cirrhosis (OR 5.07), and prolonged operation times (OR 9.61). The only risk factor for organ/space SSIs was concomitant bowel surgery (OR 5.53). Hospital stays were similar in organ/space and incisional SSI groups, but significantly longer for those with both organ/space and incisional SSIs. CONCLUSIONS: High ASA scores, anemia, chronic hepatitis or liver cirrhosis, and prolonged operations increased the risk of incisional SSIs; concomitant bowel surgery increased the risk of organ/space SSI. Specific precautions to prevent organ/space and incisional SSIs may shorten hospital stays.

Effect of selective recording on estimates of heritability

En este trabajo se analiza el efecto de la selección de datos sobre las estimaciones de heredabilidad. Se estimó el valor de heredabilidad del tamaño de camada en una población porcina en la que los datos correspondientes a las cerdas más viejas eran una muestra seleccionada. Las estimaciones se obtuvieron usando distintos conjuntos de datos derivados de toda la información disponible. Esos conjunto de datos se compararon evaluando su capacidad predictiva. Se vio que las estimaciones de heredabilidad obtenidas utilizando todos los datos disponibles correspondían a valores infraestimados. También se simuló un carácter materno y se generó un conjunto de datos seleccionados eliminando aquellos correspondientes a las hembras sin padres conocidos. Distintos modelos, habitualmente empleados cuando no existe selección de registros, se consideraron para estimar el valor de heredabilidad. Los resultados mostraron que ninguno de esos modelos ofrecía estimaciones insesgadas. Sólo los modelos que tenían en cuenta el efecto de la selección sobre la media residual y la media y varianza genéticas ofrecían estimaciones poco sesgadas. Sin embargo, para poder aplicarlos se debe conocer la selección realizada. El problema de la selección de datos es difícil de abordar cuando se desconoce cual es el proceso de selección que se ha realizado en una población.

Clustering of grape yield maps to delineate site-specific management zones

Zonal management in vineyards requires the prior delineation of stable yield zones within the parcel. Among the different methodologies used for zone delineation, cluster analysis of yield data from several years is one of the possibilities cited in scientific literature. However, there exist reasonable doubts concerning the cluster algorithm to be used and the number of zones that have to be delineated within a field. In this paper two different cluster algorithms have been compared (k-means and fuzzy c-means) using the grape yield data corresponding to three successive years (2002, 2003 and 2004), for a ‘Pinot Noir’ vineyard parcel. Final choice of the most recommendable algorithm has been linked to obtaining a stable pattern of spatial yield distribution and to allowing for the delineation of compact and average sized areas. The general recommendation is to use reclassified maps of two clusters or yield classes (low yield zone and high yield zone) and, consequently, the site-specific vineyard management should be based on the prior delineation of just two different zones or sub-parcels. The two tested algorithms are good options for this purpose. However, the fuzzy c-means algorithm allows for a better zoning of the parcel, forming more compact areas and with more equilibrated zonal differences over time.

Dose and time-dependent selective neurotoxicity induced by mephedrone in mice.

Mephedrone is a drug of abuse marketed as 'bath salts'. There are discrepancies concerning its long-term effects. We have investigated the neurotoxicity of mephedrone in mice following different exposition schedules. Schedule 1: four doses of 50 mg/kg. Schedule 2: four doses of 25 mg/kg. Schedule 3: three daily doses of 25 mg/kg, for two consecutive days. All schedules induced, in some animals, an aggressive behavior and hyperthermia as well as a decrease in weight gain. Mephedrone (schedule 1) induced dopaminergic and serotoninergic neurotoxicity that persisted 7 days after exposition. At a lower dose (schedule 2) only a transient dopaminergic injury was found. In the weekend consumption pattern (schedule 3), mephedrone induced dopamine and serotonin transporter loss that was accompanied by a decrease in tyrosine hydroxylase and tryptophan hydroxylase 2 expression one week after exposition. Also, mephedrone induced a depressive-like behavior, as well as a reduction in striatal D2 density, suggesting higher susceptibility to addictive drugs. In cultured cortical neurons, mephedrone induced a concentration-dependent cytotoxic effect. Using repeated doses for 2 days in an elevated ambient temperature we evidenced a loss of frontal cortex dopaminergic and hippocampal serotoninergic neuronal markers that suggest injuries at nerve endings.

Dose and time-dependent selective neurotoxicity induced by mephedrone in mice.

Mephedrone is a drug of abuse marketed as 'bath salts'. There are discrepancies concerning its long-term effects. We have investigated the neurotoxicity of mephedrone in mice following different exposition schedules. Schedule 1: four doses of 50 mg/kg. Schedule 2: four doses of 25 mg/kg. Schedule 3: three daily doses of 25 mg/kg, for two consecutive days. All schedules induced, in some animals, an aggressive behavior and hyperthermia as well as a decrease in weight gain. Mephedrone (schedule 1) induced dopaminergic and serotoninergic neurotoxicity that persisted 7 days after exposition. At a lower dose (schedule 2) only a transient dopaminergic injury was found. In the weekend consumption pattern (schedule 3), mephedrone induced dopamine and serotonin transporter loss that was accompanied by a decrease in tyrosine hydroxylase and tryptophan hydroxylase 2 expression one week after exposition. Also, mephedrone induced a depressive-like behavior, as well as a reduction in striatal D2 density, suggesting higher susceptibility to addictive drugs. In cultured cortical neurons, mephedrone induced a concentration-dependent cytotoxic effect. Using repeated doses for 2 days in an elevated ambient temperature we evidenced a loss of frontal cortex dopaminergic and hippocampal serotoninergic neuronal markers that suggest injuries at nerve endings.

Spatiotemporal variability in radial growth of trees in the Central Pyrenees: climatic and site influences.

To understand how tree growth has responded to recent climate warming, an understanding of the tree-climate-site complex is necessary. To achieve this, radial growth variability among 204 trees established before 1850 was studied in relation to both climatic and site factors. Seventeen forest stands were sampled in the Spanish Central Pyrenees. Three species were studied: Pinus uncinata, Abies alba, and Pinus sylvestris. For each tree, a ring-width residual chronology was built. All trees cross-dated well, indicating a common influence of the regional climate. For the 1952-1993 period, the radial growth of all species, especially P. uncinata, was positively correlated with warm Novembers during the year before ring formation and warm Mays of the year the annual ring formed. Differences in species-stand elevation modulated the growth-climate associations. Radial growth in P. uncinata at high elevation sites was reduced when May temperatures were colder and May precipitation more abundant. In the 20th century, two contrasting periods in radial growth were observed: one (1900-1949) with low frequency of narrow and wide rings, low mean annual sensitivity, and low common growth variation; and another (1950-1994) with the reverse characteristics. The increased variability in radial growth since the 1950s was observed for all species and sites, which suggests a climatic cause. The low shared variance among tree chronologies during the first half of the 20th century may result from a"relaxation" of the elevation gradient, allowing local site conditions to dominate macroclimatic influence. These temporal trends may be related to the recently reported increase of climatic variability and warmer conditions. This study emphasizes the need to carefully assess the relationships between radial growth and site conditions along ecological gradients to improve dendroclimatic reconstructions.

T cells at the site of autoimmune inflammation show increased potential for trogocytosis

Les lymphocytes T CD4+ sont connus pour leur potentiel d'acquisition de fragments membraneux de cellules présentatrices d'antigène (CPA) dans un processus nommé trogocytose. Ce phénomène est observé lors de l'interaction entre le lymphocyte T CD4+ antigène-spécifique et la CPA lors de la présentation de l'antigène en question, et dépend donc de la spécificité du lymphocyte T CD4+. L'identification des lymphocytes T CD4+ sujets à la trogocytose en co-culture avec des CPA chargées d'un antigène connu permet d'enrichir des lymphocytes T antigène-spécifiques sans connaître leur spécificité exacte ou leur profil de production de cytokines. Dans cette étude, nous avons donc cherché à évaluer l'utilité de cette méthode dans l'identification de la spécificité des lymphocytes T effecteurs et régulateurs lors de l'inflammation auto-immune avec des spécificités souvent inconnues. La trogocytose a démontré son efficacité dans la détection de lymphocytes T réactifs à la protéine basique de myéline in vitro ainsi qu'ex vivo après immunisation. Cependant, le potentiel de la trogocytose à identifier des lymphocytes T régulateurs antigène-spécifiques est limité par le fait que les lymphocytes T régulateurs Foxp3+ montrent un taux élevé de manière constitutive de trogocytose comparé aux lymphocytes T Foxp3-, Un taux localement élevé de trogocytose lors d'un état inflammatoire (observé au niveau des lymphocytes T effecteurs et régulateurs isolés du système nerveux central enflammé) empêche l'utilisation de la trogocytose dans l'évaluation de la réactivité antigénique de cellules extraites d'un site inflammatoire. Nos résultats montrent la possibilité d'enrichir des lymphocytes T conventionnels antigène- réactifs en périphérie par détection au moyen de la trogocytose. Nous avons aussi montré les limitations de cette méthode dans sa capacité d'identifier des lymphocytes T effecteurs et régulateurs antigène- réactifs extraits de sites inflammatoires. Le potentiel de trogocytose élevé dans les sites d'inflammation soulève la question de la signification biologique de ce phénomène dans l'inflammation, dans la suppression médiée par les lymphocytes T régulateurs et dans le maintien de la tolérance immunologique dans des états de santé variables.