Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

The use of 15N-labeled dietary proteins for determining true ileal amino acid digestibilities is limited by their rapid recycling in the endogenous secretions of pigs

We assessed the use of 15N-labeled dietary proteins as a possible tool for the determination of the true ileal amino acid (AA) digestibility in pigs. The first experiment was designed to study the dietary N excretion pattern at the ileum subsequent to the ingestion of a single 15N-labeled meal. In a second experiment, we compared ileal endogenous AA outputs and true AA digestibility estimates obtained in pigs ingesting 15N-labeled dietary proteins in a single meal vs. intravenous infusion of [15N]leucine for 10 d during the ingestion of a pea-based diet and a protein-free starch diet. The proportion of endogenous N found in the ileal digesta differed when the label was delivered orally (50%) vs. intravenously (72%) and changed with time. As a consequence, the true ileal AA digestibilities measured with labeled diets were lower. A third experiment demonstrated that this was due to the rapid recycling of labeled dietary N in endogenous moieties, because 15N was found in blood within 10 min of consuming the labeled meal, within 50 min of consumption in pancreatic enzymes, 90 min in bile and 4 h in ileal mucins. We conclude that the use of 15N-labeled meals for determination of true ileal AA digestibilities is limited by the fast recycling of dietary N in endogenous secretions following a single 15N-labeled meal. The accuracy of results will depend on meaningful estimates of AA flow during a limited period and accurate estimates of 15N in AA.     

Infrared spectra of poly(ethylene terephthalate) yarns. Fitting of spectra,evaluation of parameters,and applications

A quantitative model for fitting infrared spectra of polyethyleneterephthalate samples over the region from 1100 to 720 cm^?1 has been evaluated. The absorbance was described as the sum of a linear base line and a set of symmetrical bell-shaped Pearson VII curves. Using this model, experimental transmission spectra of yarns, measured with the electric vector parallel and perpendicular to the fiber axis, were fitted. It was found that each of the trans bands near 972 and 845 cm^?1 consists of two components, a narrow and a broad one. These two components represent the crystalline and amorphous phases respectively. The band due to the out of plane benzene ring C? H deformation vibration at about 875 cm^?1 appeared also to be composed of two contributions. In this case, the narrow component was found to be due to molecules having interactions with direct neighbors. So this narrow component not only contains the molecules in the crystalline phase but also those forming part of bundles which are too small to be detected by x-ray diffraction. For a detailed insight into the molecular arrangement of the amorphous regions, the infrared detection of trans-guache transitions, fold content, detection of bundlelike structures, and molecular stress on tie molecules turned out to be of great practical importance. The structural details, which can be revealed by the infrared technique, cannot be obtained by other means. The potential of the method is illustrated with some practical examples.     

Quantitative aspects of two methods to dissolve collagen-free muscle proteins from acetone dry powders of Guelders ring sausage

Summary The purpose of this study was to find experimental conditions for the complete solubility of collagen-free muscle proteins (CFMP) using acetone powder of Guelders ring sausage. Preliminary experiments were carried out to choose the best procedure for preparing the acetone dry powder. Two different methods of acetone extraction of minced sausage were compared. The acetone dry mass (ADM) method using continuous extraction in a Soxhlet [2] apparatus gave better results than the acetone powder (ACP) method, which used a blender [1]. The ADM method was used for further investigations. ADM was extracted with two types of sodium dodecyl sulphate (SDS), containing solvents A and B. Solvent A contains a Tris-boric acid buffer (pH 8.2) with 1.5% (m/v) SDS and 0.05% (m/v) dithioerythreitol [3]. Solvent B is a borate-chloric acid buffer (pH 9.0) with 2.0% (m/v) SDS and 1.0% (m/v) mercapto-ethanol [2]. Both solvents showed a linear relationship between the quantities of CFMP in ADM and the dissolved CFMP. The linear relationships were found between quantities of 10.0 and 30.0 mg (solution A) and of 5.0 and 30.0 mg ADM (solution B) per ml solvent. The solubility of CFMP was better in solvent B than in solution A. Completely dissolved CFMP from ADM was only obtained in the case of 5.0 mg ADM in 1.0 ml solution B. These conditions will be used in liquid chromatography experiments, the results of which will be reported later.

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Quantitative Aspekte zweier Verfahren für das Auflösen kollagenfreier Muskelproteine aus acetontrockenen Pulvern der Gelderschen Rauchwurst

Zusammenfassung Der Zweck dieser Untersuchungen ist, die experimentellen Bedingungen für die vollstän-dige Löslichkeit des kollagenfreien Muskelproteins (CFMP) aus dem Acetonpulver der Gelderschen Rauchwurst zu finden. Durch Vorversuche wurde die beste Arbeitsweise für das Zubereiten des Acetonpulvers gewählt. Zwei verschiedene Extraktionsverfahren mit zerkleinertem Wurstmaterial wurden miteinander verglichen. Die Methode mit der Acetontrockenmasse (ADM) mittels kontinuierlicher Extraktion [2] führte zu besseren Ergebnissen als die Methode mit Acetonpulver (ACP), wozu ein Mischgerät [1] verwendet wurde. Die ADM-Methode wurde für weitere Untersuchungen angewendet. ADM wurde mit zwei verschiedenen Extraktionslösungen von Natrium-Dodecylsulfat (SDS) (A und B) extrahiert. Lösung A enthalt einen Tris-Borsäure Puffer (pH 8,2) mit SDS (1,5%) und Dithioerithritol (0,05%) [3]. Die Lösung B enthält einen Borat-Salzsäure Puffer (pH 9,0) mit SDS (2,0%) und Mercapto-Ethanol (1,0%) [2]. Beide Extraktionslösungen zeigen ein lineares Verhalten zwischen den Mengen vom CFMP in ADM und in aufgelöstem CFMP. Diese Linearität wurde von 10,030,0 mg ADM (Lösungsmittel A) und von 5,030,0 mg ADM (Lösungsmittel B) gefunden. Die Lös-lichkeit in Lösung B ist gegeniiber Lösung A besser. Ein vollständig gelöstes CFMP aus ADM wurde nur bei der Extraktion von 5,0 mg ADM in 1,0 ml der Losung B erhalten. Diese Bedingung soll in unseren künftigen flüssigchromatographischen Experimenten verwendet werden.

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Supported by a grant from the Hoofdinspectie Levensmiddelen of the Ministry of Welzijn, Volksgezondheid en Cultuur     

What do we mean by “catalytic activity”?

The relative reactivities of the lower alkanes in hydrogenolysis on a Pt/Al₂O₃ catalyst depend on the H₂ pressure used, as do those of a Ru/Al₂O₃ catalyst, pretreated in various ways, for propane hydrogenolysis. Apparent activation energies also vary with H₂ pressure. No single rate measurement adequately represents catalytic activity, which is properly defined as the rateconstant for the slow step.     

Correct program parallelisations

International Journal on Software Tools for Technology Transfer - A commonly used approach to develop deterministic parallel programs is to augment a sequential program with compiler directives...     

VerifyThis 2015

VerifyThis 2015 was a one-day program verification competition which took place on April 12th, 2015 in London, UK, as part of the European Joint Conferences on Theory and Practice of Software (ETAPS 2015). It was the fourth instalment in the VerifyThis competition series. This article provides an overview of the VerifyThis 2015 event, the challenges that were posed during the competition, and a high-level overview of the solutions to these challenges. It concludes with the results of the competition and some ideas and thoughts for future instalments of VerifyThis.     

A process for the production of a diacylglycerol‐based milk fat analogue

We propose a novel process for the production of a DAG‐rich acylglycerol mixture derived from milk fat. This product has potentially interesting nutritional properties, derived from both its high content of DAG and of short‐chain fatty acids (FAs). The proposed process consists of three steps: lipase‐catalysed partial ethanolysis of milk fat, extraction of the by‐product fatty acid ethyl esters (FAEEs) using supercritical carbon dioxide (SC‐CO₂) and isomerization of DAG to increase the proportion of 1,3‐DAG. The experimental investigation of the process steps was done using milk fat and trilaurin. Several lipases were tested for maximizing the percentage of DAG in the acylglycerol mixture produced by ethanolysis. The selectivity of the chosen lipase was such that the produced AG mixture was enriched in short‐chain FAs in relation to the original milk fat. FAEEs were completely extracted from the ethanolysis mixture by SC‐CO₂. In the final process step, we explored the reaction conditions for facilitating acyl migration in the DAG mixture, so that the equilibrium proportion of 1,3‐DAG (～64%) was attained. Our results set the basis for the development of a simple process for the production of a DAG‐rich milk fat analogue.     

Efficiency loss prevention in monolithically integrated thin film solar cells by improved front contact

For thin film solar cells, there is a large gap between the record efficiencies and panel power output. It was found that for a “typical industrial” CIGS cell efficiency of 15.5%, the efficiency drops to 11.7% when it is operating under the circumstances of a monolithically integrated solar panel. Part of this gap is due to limited conductivity and transmittance of the front contact. By application of a metallic grid, the conductivity can be improved by over two order of magnitude at a transmittance loss of only a few percent as was shown experimentally. In addition, modeling was used to quantify the impact of such approach on the power output of monolithically integrated solar panels. This model includes optical and resistive losses, as well as related losses caused by the inhomogeneity of the operating voltage over the surface. Both power output and the different types of losses are mapped out for various cell configurations. Optimization of transparent conductive oxide resistance, cell length, finger width, and finger spacing of grids was performed and led to an efficiency improvement from 11.7% to 13.8% when the front contact is upgraded with a metallic grid consisting of 20 µm wide parallel fingers positioned perpendicular to the interconnect. Further optimization for a wide variety of cell and grid configurations show that for a technically more feasible size of 100 µm wide fingers, the calculated efficiency is still 13.5%. Finally, the power output is mapped out for a large number of configurations as to create an overview and insight in the interdependencies of cell configuration and finger dimensions. Copyright © 2014 John Wiley & Sons, Ltd.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.