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.     

Enzymatic Synthesis of Glucose- and Xylose Laurate Esters Using Different Acyl Donors,Higher Substrate Concentrations,and Membrane Assisted Solvent Recovery

Glucose- and xylose laurate esters are enzymatically synthesized using equimolar substrate concentrations in 2-methyl-2-butanol, comparing free lauric acid with methyl- and vinyl-laurate as acyl donors. All reactions result in ≥70% acyl donor conversions after 72 h but the activated donors are also partially hydrolyzed to lauric acid, highlighting the difficulty in controlling water presence in this particular reaction system. The esterification of xylose generates a complex product profile, with several regioisomers of monoesters and diesters. The esterification of glucose is quite selective, forming mainly the 6-O monoester (≥96%) with a small presence of two diester isomers (4%). Increasing substrate concentration up to 800 millimoles kg⁻¹ results in lower conversion values (down to 58%) but shows that the reaction proceeds successfully even in the presence of high amounts of insoluble glucose. However, the reaction is less selective and the proportion of diester increases, becoming up to 46% (molar fraction) of the final product. Solvent recovery after esterification can be achieved by organic solvent nanofiltration through a polymeric membrane able to retain ≥80% of all reaction substrates and products. Practical Applications: The use of high substrate concentrations during the enzymatic synthesis of sugar ester biosurfactants leads to product titers that are more industrially appealing, without the need to find a solvent that can solubilize all initial substrate. The sustainability of the enzymatic conversion at mild temperatures can be enhanced by recycling of the reaction solvent through organic solvent nanofiltration, an energy efficient alternative to other traditional methods like distillation.     

The pragmatic quality of Resources‐ Events‐Agents diagrams: an experimental evaluation

The Resources‐Events‐Agents (REA) model is a semantic data model for the development of enterprise information systems. Although this model has been proposed as a benchmark for enterprise information modelling, only few studies have attempted to empirically validate the claimed benefits of REA modelling. Moreover, these studies focused on the evaluation of REA‐based system implementations rather than directly assessing the REA‐modelled conceptual schemas that these systems are based on. This paper presents a laboratory experiment that measured the user understanding of diagrammatic conceptual schemas developed using the REA model. The theoretical foundation for the hypotheses are cognitive theories that explain pattern recognition phenomena and the resulting reduction in cognitive effort for understanding conceptual schemas. The results of the experiment indicate a more accurate understanding of the business processes and policies modelled when users recognize the REA model’s core pattern of enterprise information in the diagram. The implication for modelling practice is that the use of the REA model improves the requirements engineering process by facilitating the user validation of conceptual schemas produced by analysts, and thus helps ensuring the quality of the enterprise information system that is developed or implemented.     

Towards an international tradable green certificate system—The challenging example of Belgium

In Europe, a common framework for renewable energy sources (RES) is aspired. Tradable green certificates (TGCs) are a market-based cost-efficient means to stimulate electricity production from RES. Since TGCs are the most widespread support scheme in Europe together with feed-in tariffs, chances are that a common European framework could well be based on TGCs. However, while integrating currently existing different national TGC systems, any remaining differences should be carefully considered. Just how difficult the creation of an international TGC market would be is illustrated in this paper by the case of Belgium, where no less than 4 different TGC systems exist nowadays. The example of Belgium illustrates that harmonizing different TGC systems is easier said than done and represents a serious challenge. This clearly illustrates that a single European support scheme for RES, however desirable, is still far in the future.     

Non-hydrothermal synthesis of copper-, zinc- and copper-zinc hydrosilicates

Cu/SiO₂, Zn/SiO₂ and Cu-Zn/SiO₂ samples have been prepared by the homogeneous deposition-precipitation method. The samples were analyzed by thermal analysis, X-ray diffraction and infrared spectroscopy after various heat treatments and compared with data obtained for several minerals. It has been shown that interaction between the components occurs through formation of hydrosilicates. Copper-silica system at a Cu:Si ratio ≤ 1, gives rise to a hydrosilicate stable up to a calcination temperature of 930 K resembling the mineral Chrisocolla; at higher ratios a hydroxonitrate (gerhardite type) is also formed. Zinc-silica interaction produces two hydrosilicates such as a well crystallized Hemimorphite at Zn:Si = 2 and highly dispersed Zincsilite at Zn:Si ≤ 0.75, both stable up to 1073 K. The Zincsilite structure consists of three layered sheets (an octahedral layer sandwiched by two tetrahedral ones) like the Stevensite mineral group. For the copper-zinc-silica system no copper hydrosilicate is formed. Copper merely enters the Zincsilite structure independenly of the applied (Cu + Zn):Si ratio. Resulting layered copper-zinc hydrosilicate may be described by formula Zn_x-yCu_y(Zn_3-x–zCu_z–y▪_x)[Si₄O₁₀](OH)₂.nH₂O, where Zn_3-x-zCu_z-y– ions are located in octahedral sites, Zn_x-yCu_y–ions in the interlayer; ▪_x are vacancies in the layers. Copper and zinc in excess of the Zincsilite ratio of Me:Si = 0.75, gives rise to copper and copper-zinc hydroxonitrates. Received: 7 November 2000 / Reviewed: 23 January 20001 / Accepted: 23 January 2001     

Technological and economical aspects of the metathesis of unsaturated esters

The metathesis of alkenes is a well-established reaction that is applied in various commercial processes. The meta-thesis of functionalized olefins has not yet been commercialized despite its considerable potential. The conversion of oleochemical feedstocks into specialty chemicals appears especially attractive. In this paper, a process scheme is proposed for the production of 1,18-dimethyl octadecanedioate from pure methyl oleate by metathesis. The chemical and technological bottlenecks are explored, and a rough economic evaluation of this route is given. From these considerations, it is concluded that such a process for the metathesis of functionalized alkenes could be viable only if certain conditions are met. Rapid catalyst deactivation is identified as one of the main obstacles. Feedstock purity, efficient recycling of unreacted feed and multiple catalyst regeneration are crucial for economic feasibility. Rhenium-based catalysts are to be preferred over molybdenum ones because their activation is easier and regenerability is superior. Finally, the direction for future technological and catalysis research is given based upon the results of this work.     

Cerebrospinal fluid methylmalonic acid concentrations in neurological patients with low and normal serum cobalamin concentrations

OBJECTIVE: To determine whether cerebrospinal fluid (CSF) methylmalonic acid (MMA) is increased in neurological patients with low serum cobalamin (Cbl, vitamin B12) concentrations as opposed to neurological patients with normal serum Cbl concentrations. MATERIAL AND METHODS: We measured MMA concentrations in serum and CSF of neurological patients with low serum cobalamin concentrations, but without overt cobalamin related manifestations such as anemia or combined disease of the cord, and neurological patients with normal serum cobalamin concentrations (controls). RESULTS: Serum and CSF MMA concentrations were significantly higher in patients than in controls. Serum MMA was elevated in 4 patients of whom 3 had clearly elevated CSF MMA concentrations. CONCLUSION: Strong indications for cobalamin deficiency can be found not only in serum but also in CSF of patients with seemingly asymptomatic low serum cobalamin concentrations.     

Oral omega-6 essential fatty acid treatment in contact lens associated dry eye

PURPOSE: Symptoms of dry eye are commonly reported in contact lens wearers and are a frequent cause of non-tolerance. The purpose of the present study is to evaluate the effects of oral treatment with particular omega-6 fatty acids in the form of evening primrose oil (EPO) on subjective symptoms, ocular surface signs and tear film characteristic in patients with contact lens associated dry eye. METHODS: The study design was randomised, double-masked and placebo controlled. 76 female soft contact lens wearers were treated for 6 months with either EPO or placebo (olive oil). Subjects underwent three examinations (baseline, 3 and 6 months). At each examination subjects were given a questionnaire relating to lens comfort and dry eye symptoms and underwent a series of tests of tear film characteristics (tear meniscus height, break-up time), meibomian gland function (lipid layer thickness and quality) and ocular surface parameters (hyperaemia and staining). RESULTS: The EPO group showed a significant improvement in the specific symptom of 'dryness' at 3 and 6 months (p<0.01) and also a significant improvement in overall lens comfort at 6 months (p<0.01). Tear meniscus height was increased in the EPO group at 6 months relative to baseline (p<0.01), although all other objective signs were unchanged. CONCLUSION: This study provides evidence for a beneficial effect of particular orally administered omega-6 fatty acids in alleviating dry eye symptoms and improving overall lens comfort in patients suffering from contact lens associated dry eye.     

Automated conceptual model clustering: a relator-centric approach

Software and Systems Modeling - In recent years, there has been a growing interest in the use of reference conceptual models to capture information about complex and sensitive business domains...     

Solvent-based fatty alcohol synthesis using supercritical butane: Flowsheet analysis and process design

The liquid-phase hydrogenolysis of fatty esters to fatty alcohols is an important step in the industrial manufacture of surfactants and detergents. High operating pressures are necessary, due to the low solubility of hydrogen in fatty esters feeds. In principle, these high operating pressures might be overcome by use of a suitable solvent, but only at the expense of large solvent recycle and cumbersome product-solvent separation. The employ of supercritical solvents may resolve these drawbacks, as an elegant solvent-product separation is possible by reverting to the subcritical regime. In the present work the hydrogenolysis of methyl palmitate in supercritical butane is investigated by simulation. Operating conditions are analyzed on the basis of vapor liquid equilibrium data and chemical equilibrium considerations. Separation and recycle problems are evaluated and discussed on the basis of a flowsheet analysis. It is demonstrated that an efficient hydrogenolysis process may be developed by using supercritical butane as solvent. A moderate operating pressure (9 MPa) and temperature (470 K) lead to high conversion levels and high product purity. A hydrogen to ester molar ratio of 4∶1 in the feed is achievable, which compares favorably to existing liquid-and gas-phase processes, and allows recycle streams to be reduced.