Perovskite-based catalysts for tar removal by steam reforming: Effect of the presence of hydrogen sulfide

One of the greatest problems in biomass gasification processes is the conditioning of the produced synthesis gas, which contains various contaminants, including tar and hydrogen sulfide. Nickel catalysts, designed for steam reforming of aliphatic hydrocarbons (natural gas and nafta), are usually deactivated by coke deposition and sulfur poisoning. In this work, nickel and/or manganese catalysts derived from perovskites were prepared by the citrate method and characterized by X-ray diffraction, N₂ physisorption and temperature programmed reduction. The catalysts were evaluated in the steam reforming of toluene, used as tar model compound, in the absence of H₂S at 700 °C and in the presence of 50 ppm H₂S at 800 °C. LaNi_0.5Mn_0.5O₃ catalyst showed higher activity and stability in the absence of H₂S. LaMnO₃ catalyst, although less active in the absence of H₂S, showed increased stability in the presence of H₂S, with conversion of about 60%. H₂ production was only observed in the absence of H₂S.     

Influence of Cu<Superscript>2+</Superscript> ions on structural and magnetic properties of NiZn ferrites

The paper is devoted to the preparation of NiZn ferrite with small substitutions of copper by means of ceramic technology. The influence of small Cu substitution on the microstructural and magnetic properties of NiZn ferrites have been analysed by means of various experimental methods and interpreted from the point of view of preparation technology optimisation and possible applications of such materials. A strong correlation between the substituent content and resulting properties has been observed, thus allowing preparation of material with the properties tailored for any particular application.     

Variation in the molecular mass of exopolysaccharides during the time course of extended fermentations of skimmed milk by lactic acid bacteria

The weight average molecular mass (M_w) of the exopolysaccharide (EPS) secreted by Lactobacillus acidophilus 5e2 when grown on skimmed milk supplemented by glucose was monitored during extended fermentation times. During the exponential growth phase, the increase in M_w closely followed the increase in yield of EPS. Under the fermentation conditions applied in this study, few if any new polysaccharide chains were formed during this growth phase despite a twenty five-fold increase in the cell count; almost the entire increase in yield can be accounted for by an increase in chain length. These results suggest that synthesis of new EPS chains is switched off during the exponential and stationary phase of fermentation. The increase in yield observed in this period is a consequence of the bacteria's ability to extend existing chains right up to the mid-stationary phase. These results raise questions about the factors that control EPS production and chain length.     

Functional polysiloxanes

Summary Carboxyester- and carboxyamido-terminated polydimethylsiloxanes were obtained through the reaction of cyclic anhydrides (succinic, maleic and phthalic anhydride) with hydroxypropyl- and aminoalkyl-terminated polydimethylsiloxanes, respectively. The reactivity of the starting compounds and the influence of the reaction conditions on the characteristics of the final products are discussed.Part 1: Eur. Polym. J., in press     

Natural silica fiber as reinforcing filler of nylon 6

Short silica fiber (SF) content on the mechanical and morphological properties of composites based on nylon 6 and rubber-toughened nylon 6 matrices was examined. Binary nylon 6/SF and ternary [nylon 6/EPDM-g-MA (ethylene–propylene–diene grafted with maleic anhydride)/SF] composites containing 0–20 wt% SF were formulated. The flexural modulus increased with the SF content at all fiber compositions investigated; however, the value of this property gradually diminished when 20 wt% rubber was added to the polymer. Notched Izod impact strength of 80/20 nylon 6/EPDM-g-MA blend was reduced up to 50% with the addition of 5 wt% SF. However, these composites still retained good stiffness and toughness and presented a good interfacial adhesion between the phases. The results suggest that silica fibers can be employed as an alternative reinforcement of nylon 6 matrices, resulting in materials with useful properties.     

Structure–property relationship of sodium deoxycholate based poly(ester ether)urethane ionomers for biomedical applications

New sodium deoxycholate based poly(ester ether)urethane ionomers were prepared for the development of biomedical materials. A structure–property relationship in the tested biomaterials was established by cross‐examination of the dynamic mechanical and dielectric properties, attenuated total reflection–Fourier transform infrared investigation, thermogravimetric analysis, and surface morphology characterization. A stronger ionic interaction and solvation capacity of the ions and a higher ionic conductivity were manifested in the case of poly(ethylene oxide)‐rich segments than for poly(propylene oxide)‐rich segments in these polyurethane ionomers. The molecular and ionic interactions of the bile‐salt moiety with different polyether cosoft segments influenced chain packing and conformation, supramolecular organization, and the resulting surface morphological microstructures of the polyurethane biomembranes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42921.     

3D printed millireactors for process intensification

The scope of the present research aims at demonstrating the 3D printing use in the manufacturing of microchannels for chemical process applications. A comparison among digital model processing applications for 3D print(slicers) and a print layer thickness analysis were performed. The 3D print fidelity was verified in several devices, including the microchannels' printing with and without micromixer zones. In order to highlight the 3D print potential in Chemical Engineering, the biodiesel synthesis was also carried out in a millireactor manufactured by 3D printing. The millireactor operated under laminar flow regime with a total flow rate of 75.25 ml ? min~(-1)(increment of about 130 times over traditional microdevices used for biodiesel production).The printed millireactor provided a maximum yield of Ethyl Esters of 73.51% at 40 °C, ethanol:oil molar ratio of7 and catalyst concentration of 1.25 wt% and residence time about 10 s. As a result of flow rate increment attained in the millireactor, the number of required units for scaling-up the chemical processes is reduced. Using the approach described in the present research, anyone could produce their own millireactor for chemical process in a simple way with the aid of a 3D printer.     

Structural and thermal behavior of 45S5 Bioglass®-based compositions containing alumina and strontium

The present research exposes the influence of 2 mol% of Al₂O₃ and 2 mol% SrO in 45S5 Bioglass^®-based compositions. Four compositions were produced to elucidate the difference in how both oxides influence structure and thermal behavior separately and their synergy when together. Thermal properties, crystallization tendency, and sintering behavior was evaluated by differential scanning calorimetry, hot stage microscopy, and dilatometry. Changes of medium-range structures were characterized by Qⁿ distribution of Raman spectroscopy and evaluation of ³¹P, ²⁷Al, ²³Na, and ²⁹Si environment obtained by magic angle spinning nuclear magnetic resonance. Despite Qⁿ distribution was predominantly Q² in all samples, the composition criteria used enabled improved processing and stabilibity characteristics. The addition of Al₂O₃ and SrO promoted larger sinterability parameter (S_c) which indicates better sintering behavior, the glass stability against crystallization doubled (K_H) compared to 45S5 and the processing window enlarged from 106 to 171.     

Interspecific Cross-Attraction between the South American Cerambycid Beetles <Emphasis Type="Italic">Cotyclytus curvatus</Emphasis> and <Emphasis Type="Italic">Megacyllene acuta</Emphasis> is Averted by Minor Pheromone Components

During field screening trials conducted in Brazil in 2015, adults of both sexes of the cerambycid beetles Cotyclytus curvatus (Germar) and Megacyllene acuta (Germar) (subfamily Cerambycinae, tribe Clytini) were significantly attracted to racemic 3-hydroxyhexan-2-one and racemic 2-methylbutan-1-ol, chemicals which previously have been identified as male-produced aggregation-sex pheromones of a number of cerambycid species endemic to other continents. Subsequent analyses of samples of beetle-produced volatiles revealed that males of C. curvatus sex-specifically produce only (R)-3-hydroxyhexan-2-one, whereas males of M. acuta produce the same compound along with lesser amounts of (2S,3S)-2,3-hexanediol and (S)-2-methylbutan-1-ol. Follow-up field trials showed that both sexes of both species were attracted to synthetic reconstructions of their respective pheromones, confirming that males produce aggregation-sex pheromones. The minor pheromone components of M. acuta, (S)-2-methylbutan-1-ol and (2S,3S)-2,3-hexanediol, synergized attraction of that species, but antagonized attraction of C. curvatus to (R)-3-hydroxyhexan-2-one. Beetles of other cerambycine species also were attracted in significant numbers, including Chrysoprasis linearis Bates, Cotyclytus dorsalis (Laporte & Gory), and Megacyllene falsa (Chevrolat). Our results provide further evidence that 3-hydroxyhexan-2-one is a major component of attractant pheromones of numerous cerambycine species world-wide. Our results also highlight our increasing understanding of the crucial role of minor pheromone components in imparting species specificity to cerambycid pheromone blends, as is known to occur in numerous species in other insect families.     

Combustion synthesis of copper catalysts for selective CO oxidation

Copper catalysts supported on ceria, zirconia and niobia were prepared by combustion method with urea, containing a CuO loading of 6 wt.%, and tested on selective oxidation of CO. The characterization of the samples by X-ray diffraction (XRD) presented the formation of solid solution on CuO–CeO₂ catalyst and a change in crystalline structure of the support with copper insertion on ZrO₂ and Nb₂O₅ catalysts. The analysis of temperature-programmed reduction (TPR) revealed different interaction degrees of copper with the supports, with reduction peaks between 222 and 390 °C. The temperature-programmed desorption of CO (TPD-CO) profiles showed formation of CO₂ and H₂ only for the ceria and zirconia catalysts. In relation to the catalytic tests, the CuO–CeO₂ catalyst presented the best performance, with CO conversion of 95% at 150 °C up to 45 h on stream, and CO₂ selectivity of 55%.