A range of polyimides with characteristics similar to a polymer of intrinsic microporosity (PIM) were prepared by reaction with various aromatic diamines of a bis(carboxylic anhydride) incorporating a spiro-center. The polymers exhibited high surface area, as determined by nitrogen adsorption, and high thermal stability. Membrane gas permeation experiments showed PIM-polyimides to be among the most permeable of all polyimides and to have selectivities close to the upper bound for several important gas pairs. A group contribution method was used to predict permeability coefficients and separation factors for further PIM-polyimide structures, revealing worthwhile targets for future synthetic efforts.
The influence of hydrogen on the catalytic deoxygenation of fatty acids was investigated in the semibatch reactor over a mesoporous 5 wt % Pd/C (Sibunit) catalyst. Transformations of a model fatty acid (lauric acid) and reaction intermediates (lauric aldehyde and lauryl alcohol) were performed under inert and hydrogen rich atmosphere. Analysis of the liquid and gas phases of the reaction mixture revealed that different reactions occurred depending on hydrogen content in the reaction atmosphere. A higher yield of hydrocarbons (59 mol %) was obtained in the fatty acid deoxygenation under hydrogen pressure compared to an experiment under argon where the yield of hydrocarbons reached 39 mol % after 300 min of the reaction. Different product distributions, intermediates and reaction pathways depending on hydrogen content in the reaction atmosphere, are discussed.
Aqueous phase reforming of sorbitol over Pt supported on an alumina catalyst is investigated, in order to identify the intermediates involved in the transformation of the initial feed. Parameters such as the sorbitol feed rate and temperature are studied. To identify the intermediates, an approach based on analysis of the gas and liquid phases as well as the total carbon content was developed. According to analysis by gas chromatography combined with mass spectrometry of volatile substances collected with solid-phase microextraction, over 260 compounds are involved in the transformation of sorbitol. Of these, 50 of the major products are identified with high reliability. It is shown that a great variety of compounds, bearing different functionalities, form part of the reaction network. The formation of the majority of identified compounds is explained and a reaction network for the formation of sorbitol and intermediate molecules transformation is proposed.
High catalytic activity was achieved in the deoxygenation of stearic acid in dodecane in a temperature range of 270-300°C under 17 bar helium over palladium on nanocomposite carbon Sibunit. Besides n-heptadecane, which was obtained previously in this reaction with palladium on activated carbon, n-pentadecane was also formed in significant amounts.
aThe aqueous phase reforming (APR) of xylitol was studied over five Pt/C catalysts. The correlation between physico-chemical properties of the catalysts and catalytic performance was established. The Pt/C catalysts have different textural properties as well as different mean Pt cluster sizes and surface acidity. The average Pt cluster size was investigated by means of CO chemisorption as well as by TEM.The reaction was found to be structure sensitive and TOF linearly increases with increasing average Pt cluster size in the studied domain. The catalysts which possess higher surface acidity favoured higher rates of hydrocarbon production. On the contrary the Pt/C materials with lower acidities generated hydrogen with high selectivity and TOF.
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