Biobutanol Dehydrogenation to Butyraldehyde over Cu,Ru and Ru–Cu Supported Catalysts. Noble Metal Addition and Different Support Effects

Abstract  

n-Butanol dehydrogenation to butyraldehyde was studied using Ru, Cu and Ru–Cu catalysts supported on ceria, titania and zirconia. Among the monometallic Cu and Ru supported catalysts, the non-noble catalytic systems recorded higher conversions and butyraldehyde selectivities than the noble catalysts. Furthermore, the 5Cu/ZrO₂ catalyst had the best catalytic activity and selectivity. This behaviour is related to the good metal phase dispersion on the zirconia structure. The addition of Ru reduced this catalyst’s performance because Ru incorporation weakened the Cu-support interaction and favoured the sintering of the Cu metal crystallites.     

Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde

The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic ion exchange resin was studied. These acetals can be obtained from renewable sources (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for different applications such as oxygenated diesel additives. A preliminary kinetic study was performed in a batch stirred tank reactor studying the influence of different process parameters like temperature, feed composition and the stirring speed. A pseudo homogenous kinetic model able to explain the reaction mechanism was adjusted. Thus, the corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin showed a fairly good behavior allowing 100% of selectivity towards acetals formation. However, the studied acetalization reaction showed high thermodynamic limitations achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed.     

Process integration for hydrogen production,purification and storage using iron oxides

Hydrogen production from natural gas using a Ni-based catalyst and its later hydrogen storage with some synthetic and natural iron oxides are presented. The Ni-based catalyst showed high methane conversion, close to the equilibrium one, when producing hydrogen from methane through catalytic partial oxidation (CPO) and wet-CPO with a low steam to carbon ratio (0.5). The solid solution formation observed in the Ni-based catalyst could have enhanced its stability. The iron oxides capacity for hydrogen storage was analysed with reduction–oxidation cycles at 973 K and atmospheric pressure. The natural oxides presented structural modifications, mainly due to sinterization, which negatively affected their storage capacity and stability.     

Practical issues in self-observation.

Using self-observation as a clinical or research tool requires attention to a number of practical concerns. In this article, issues involved in selecting a self-observation method are considered, including determining the dimension of behavior to be observed and choosing a method and recording device for sampling behavior. The literature on training individuals to self-observe, which supports the importance of comprehensive multicomponent training, is surveyed. Also considered are ways of evaluating and improving data quality as the self-observer collects information and of engineering compliance with requests to self-monitor. Future research should (a) systematically examine ways of obtaining high-quality self-observation data and enhancing participant compliance and (b) extend findings of older investigations both to contemporary methods of collecting information and to self-observation of private events. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A visual tool for monitoring and detecting anomalies in robot performance

Pattern Analysis and Applications - In robotic systems, both software and hardware components are equally important. However, scant attention has been devoted until now in order to detect...     

Hydrothermal stability improvement of NiPt-containing γ-Al2O3 catalysts tested in aqueous phase reforming of glycerol/water mixture for H2 production

The hydrothermal stability of Ni and NiPt-containing γ-Al₂O₃ catalysts in aqueous phase reforming (APR) of glycerol/water mixture (C₃H₈O₃/H₂O, 10% w/w) was investigated putting in evidence the influence of the preparation method; sol–gel in basic medium (SGB) and impregnation on an in-house prepared sol–gel γ-Al₂O₃ support (SGI). All developed catalysts were characterized by ICP-AES, TPR-H₂, in-situ heating XRD-O₂, DSC/TG-N₂/O₂ and ex-situ reduction of XRD-H_2, N₂ physisoption and TEM techniques. The results indicate that SGI method and calcination treatment at 750 °C were crucial in extending the catalytic useful life of NiPt-containing γ-Al₂O₃ catalysts, resulting in an adequate distribution of NiPt metallic particles and good stability of γ-Al₂O₃ support against the severe hydrothermal conditions of APR process. The SGI method led to form stable NiPt catalysts with relatively big Ni particles and stable hydrothermal properties of γ-Al₂O₃ support, while the SGB catalysts exhibited well-dispersed Ni particles but unstable catalytic behavior. These last catalysts presented high glycerol conversions during the first hours of APR glycerol/water reaction, however, an important decrease in terms of glycerol conversion was observed after 24 h time-on-stream. The experimental results suggested that the most suitable stable and active catalyst was the NiPt/ASGI7 (better than >NiPt/ASGI6 > NiPt/ASGI5 >>> NiPt/ASGB7). This catalyst showed best catalytic activity and good catalytic stability along 56 h of time-on-stream, reaching, at steady state, highest total glycerol conversion (≈79%) and glycerol into gaseous products (≈57%) in APR reaction of glycerol/water mixture for hydrogen generation.     

Recycling of the Products Obtained in the Pyrolysis of Fibre-Glass Polyester SMC

An SMC (Sheeting Moulding Compound) of fibre-glass and orthophthalic polyester has been pyrolysed in a 3·5 dm³ autoclave for 30 min in a nitrogen atmosphere at 300, 400, 500, 600 and 700°C. Gas yields of 8–13 weight%, liquid yields of 9–16 weight% and solid residues of 72–82 weight% were obtained. The suitability of the pyrolysis process for recycling SMC is discussed. The characteristics, compositions and possible ways of reusing the liquid and gaseous fractions are presented. The solid pyrolysis residue has been recycled in another thermoset composite (Bulk Moulding Compound, BMC) and its mechanical properties have been compared with those of virgin BMC. The main conclusion is that pyrolysis can be an appropriate method for recycling thermoset polymeric composites such as SMC. The pyrolysis gas fraction can be sufficient to provide the energy requirements of the process plant. The pyrolysis liquids have high gross calorific values (36·8 MJ kg⁻¹) and are non-polluting liquid fuels; about 40 weight% of such liquids could be used as petrols, and the remaining 60% could be mixed with fuel oils. The solid pyrolysis residue can be recycled in BMC with no detrimental effect on the BMC mechanical properties. Concerning temperature, it has been concluded that 400–500°C are the most suitable temperatures for recycling SMC by pyrolysis. © 1997 SCI.     

Biohydrogen production by gas phase reforming of glycerine and ethanol mixtures

In this paper the steam reforming of bioalcohols over Ni and Pt catalysts supported on bare Al₂O₃ and La₂O₃ and CeO₂-modified Al₂O₃ to produce H₂ was studied. Catalytic activity results showed that the glycerine and the intermediate liquid products may hinder the ethanol adsorption on metal active sites of the catalysts, especially at temperatures below 773 K. In fact, ethanol conversion was lower than glycerine conversion in the steam reforming reaction at low temperatures. H₂ chemisorption revealed that La₂O₃ doping of the Ni/Al₂O₃ catalyst improved the metal dispersion providing a better behaviour to the Ni/Al₂O₃-O2 catalyst towards H₂ production. In the case of Pt catalysts, the good reducibility and the H₂ spillover effect provided to the Pt/Al₂O₃-O1 catalyst the capacity to produce higher H₂ yields.     

Effect of ZrO2 addition on Ni/Al2O3 catalyst to produce H2 from glycerol

In this work, ZrO₂ was employed as support and as Al₂O₃ modifier of Ni based catalysts due to its special interesting characteristics. The catalytic activity of these systems was studied in steam reforming of glycerol to produce H₂. As the activity results at 773 K and 873 K showed, the NiZ catalyst allowed low glycerol conversion and H₂ production when compared to the NiγA catalyst. Moreover, the NiZ catalyst was not able to reform intermediate liquid products into gaseous products.     

Copper deposition on Pd membranes by electroless plating

PdCu membranes were prepared by the electroless plating of Pd membranes prepared on ceramic tubular supports. Different PdCu membranes were prepared with Pd content between 45 and 77 wt% and a total metal layer between 0.5 and 1.9 μm thickness. The alloying step was performed in two ways to compare and establish the required alloying time for obtaining high permeance membranes. The alloying was analysed with EDX composition measurements, and full alloying was not required to obtain a stable hydrogen flux. Finally, permeance tests were performed at different pressures, including temperature cycles in hydrogen and nitrogen, to observe membrane stability. The hydrogen permeance values of the membranes were high, between 1.5 × 10⁻³ and 4.5 × 10⁻³ mol/(s Pa^0.5 m²) at 673 K. The membranes recorded stable permeance values even after thermal cycles in a hydrogen atmosphere. Metal layer thickness was calculated using both the weight difference method and SEM images. SEM images were also used to analyse the surface morphology of the membranes, which was generally fairly uniform and smooth.