Photo-Chemically-Deposited and Industrial Cu/ZnO/Al2O3 Catalyst Material Surface Structures During CO2 Hydrogenation to Methanol: EXAFS,XANES and XPS Analyses of Phases After Oxidation,Reduction, and Reaction

Catalysis Letters - Industrial Cu/ZnO/Al2O3 or novel rate catalysts, prepared with a photochemical deposition method, were studied under functional CH3OH synthesis conditions at the set temperature...     

Nonoxidative methane activation,coupling, and conversion to ethane,ethylene, and hydrogen over Fe/HZSM‐5, Mo/HZSM‐5, and Fe–Mo/HZSM‐5 catalysts in packed bed reactor

A high abundance of methane and its relatively low price make it an attractive raw feedstock for the production of ethylene, which is in the consumer demand in recent years. Direct catalytic nonoxidative conversion is interesting, because it could be utilized on natural gas well sites. Monometallic and bimetallic Fe and Mo catalysts were prepared for the purpose of the coupling to ethane and ethene. Three supported materials were synthesized with the following loading of metal: 2.5‐wt% Fe, 5.0‐wt% Fe, and 2.5‐wt% Mo on HZSM‐5. Process' chemical reactions were also catalyzed with a constant 2.5‐wt% Mo/HZSM‐5, which had different amounts of Fe, namely, 0.5, 1.0, and 2.5 wt%. Fourier transform infrared (FTIR), N₂ adsorption/desorption, NH₃ temperature‐programmed desorption (TPD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were applied for characterization. Coke, accumulated on spent solids, was determined by thermogravimetric analysis (TGA). Activity was evaluated in quartz‐packed bed reactor. All surfaces suffered from deactivation due to carbon formation. The addition of Fe to Mo increased CH₄ reacted. The highest selectivity for alkenes was achieved over 1.0‐wt% Fe to 2.5‐wt% Mo/HZSM‐5. At the peak of performance, the C‐based reactivity was 52% for olefins and 2% for alkanes. Stability was accomplished over 2.5‐wt% Fe/HZSM‐5, where the rate of C₂ synthesis was comparatively stable for 20 hours of the time on stream. The selective C‐basis yield for C₂H₄ and C₂H₆ was 36% and 23%, respectively. The lowest measured quantity of (carbonaceous) by‐products was deposited on 2.5‐wt% Fe/HZSM‐5 after 26 hours. Propylene was detected very limitedly.     

HPLC–MS identification of phenols in hazelnut (Corylus avellana L.) kernels

In whole hazelnut kernels, as the main product of hazelnut (Corylus avellana L.), phenols were analysed in 20 hazelnut cultivars by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS). Twenty-three compounds from different phenolic groups were detected, and 15 of them were identified. In hazelnut kernels, these substances were detected: nine flavan-3-ols, two benzoic acids (gallic and protocatechuic acid), three flavonols and phloretin glycoside. Total phenol concentrations ranged from 70 to 478 mg gallic acid equivalents per kg hazelnut kernels. A high content level of total phenols was observed in the ‘Tonda Gentile delle Langhe’ and ‘Lewis’ cultivars, which was followed by the ‘Corabel’, ‘Fertile de Coutard’, ‘Daria’ and ‘Tonda Gentile Romana’ cultivars. Similarly, the highest antioxidative activity, measured by employing DPPH-antiradical assay, was also found in the ‘Tonda Gentile delle Langhe’ cultivar, followed by the ‘Fertile de Coutard’.     

Modeling of dynamic mechanical properties of vulcanized fluoroelastomer

The dynamic mechanical properties of a vulcanized fluoroelastomer (FKM) were studied over a range of temperatures and shear frequencies. Dynamic mechanical analysis and differential scanning calorimetry were used for the purpose of the study. A model was developed in order to describe FKM's viscoelastic behavior at various temperatures. The model was fitted to experimental data using an algorithm, which was developed for this purpose. As a result the FKM discrete relaxation spectrum at two reference temperatures was obtained, as well as the Williams‐Landel‐Ferry (WLF) equation parameters or the activation energy equivalent. Further on, the model was applied on storage modulus and loss tangent values obtained from the experiments, during which the temperature increased linearly. It was observed that the WLF equation fits well with the results during the glass transition, while the Arrhenius‐type relationship predicted too rapid decrease of the storage modulus during the glass transition. The master curves were constructed using the previously calculated WLF parameters and the activation energy equivalent. The developed model may be readily applied for the prediction of the numerous FKM compounds' frequency–temperature behavior using the dynamic mechanical properties obtained from either isothermal or low linear heating rate program measurements. POLYM. ENG. SCI., 47:2085–2094, 2007. © 2007 Society of Plastics Engineers     

The influence of the polymerization on properties of an ethylacrylate/2-ethyl hexylacrylate pressure-sensitive adhesive suspension

In this paper, the batch suspension copolymerization process for production of microsphere acrylic pressure-sensitive adhesives (PSA) is presented. The effects of different process and chemical parameters on adhesion properties are discussed. The reaction was monitored in-line by using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Properties of the adhesive suspension (particle size), adhesive (gel phase, molecular weight, glass transition temperature (T_g)) and adhesion properties (tack, peel strength and shear) were determined. The results have shown that reaction kinetics strongly depends on polymerization temperature and initiator concentration. On the other hand, adhesion properties depend mainly on the T_g of the polymer and on the amount of insoluble gel fraction in the adhesive.     

Plasma‐activated methane partial oxidation reaction to oxygenate platform chemicals over Fe,Mo, Pd and zeolite catalysts

Natural gas from stranded sources is being predominantly flared, and there is a growing demand for new technologies for its utilisation, where electrification, flexibility, and modularity play an important role. Plasma‐activated methane partial oxidation reaction was studied in a designed dielectric barrier discharge ionisation reactor unit, producing value‐added platform chemicals, namely, methanol, formaldehyde, intermediate formic acid, acetic acid, and paraformaldehyde at ambient temperature and atmospheric pressure. The effects of various process parameters, such as voltage, total convertible gas flow rate, and reagent ratio relationship, were considered. In addition, coupling of the following catalytic materials with plasma was examined: alumina (Al₂O₃), chabazite, ferrierite, microporous beta zeolite, silica (SiO₂) glass beads, ZSM‐5 (MFI), Fe on H‐ZSM‐5 and Al₂O₃, Mo on H‐ZSM‐5, TiO₂ and SiO₂, and Pd on Al₂O₃. In the liquid product, 21.5% CH₃OH, 20.4% CH₂O, 0.3% HCOOH, and 2.4% CH₃COOH were measured when using pure plasma, and a maximum aggregate yield of the organic oxygenate compounds of 5.21 mol.% was achieved. The usage of shaped silicate surface increased the selectivity towards synthesised oxygen‐containing structures, while the application of alumino‐silicate mixture constituents reduced it. It was determined that elementary covalently bonded carbon was formed inside pores when pure zeolites were used. Fe‐ and Pd‐based heterogeneous catalysts favoured the complete exothermic combustion of CH₄ feedstock reactant species, and the liquid product consisted only of water in the Pd‐ case. The utilisation of Mo/H‐ZSM‐5 resulted in a 46% increased yield of formalin. A mechanism for the role of Mo was proposed, where Mo oxidises methanol to formaldehyde and the metal is reoxidised in plasma.     

Active chitosan–chestnut extract films used for packaging and storage of fresh pasta

A tannins-rich chestnut extract was used to enhance the antioxidant and antibacterial properties of chitosan-based film materials. The favourable mechanical properties of the novel material enabled its application in the preparation of the sachets that were used for packing and storage of filled fresh pasta. The fresh pasta ageing progressed in conventional refrigerated storage conditions of 8 °C with 60 ± 2% relative humidity in the absence of light for 60 days. The rapid moisture mobility between a starchy food and sachets during the first 9 days of storage induced retrogradation of the fresh pasta, whereby total phenolic content show dependency on moisture throughout the shelf life. Active components within the sachet prevented microbial growth on the food surface during the entire 60 days.     

Hydrodynamics,mass transfer,and photocatalytic phenol selective oxidation reaction kinetics in a fixed TiO2 microreactor

Photocatalytic phenol dissociation was studied in a microreactor, with a TiO₂ layer immobilized on the reactor inner walls. Experiments were conducted for various residence times, initial concentrations, pH values, and UV light irradiation intensities. The intermediates and products (catechol, hydroquinone, and resorcinol) were quantitatively investigated to determine the predominant reaction pathways for the investigated anatase catalyst. A three‐dimensional mathematical model was used to simulate the heterogeneous photocatalysis reaction conditions with Langmuir–Hinshelwood mechanism, considering the adsorption/desorption thermodynamic equilibria, and for kinetic parameter estimation via regression analysis. The effectiveness factor, Thiele modulus, and the correction function were calculated to determine the pore diffusion effects. The value of pH had the dramatic effect of lowering the reaction rate due to the competitive adsorption of hydroxide ions and protons on the catalyst surface. A phenol conversion of 79.5% was achieved at the residence time of 7.22 min, but without total mineralization. © 2014 American Institute of Chemical Engineers AIChE J, 61: 572–581, 2015     

Optimization of Ligninolytic Enzyme Activity and Production Rate with Ceriporiopsis subvermispora for Application in Bioremediation by Varying Submerged Media Composition and Growth Immobilization Support

Response surface methodology (central composite design of experiments) was employed to simultaneously optimize enzyme production and productivities of two ligninolytic enzymes produced by Ceriporiopsis subvermispora. Concentrations of glucose, ammonium tartrate and Polysorbate 80 were varied to establish the optimal composition of liquid media (OLM), where the highest experimentally obtained activities and productivities were 41 U L⁻¹ and 16 U L⁻¹ day⁻¹ for laccase (Lac), and 193 U L⁻¹ and 80 U L⁻¹ day⁻¹ for manganese peroxidase (MnP). Considering culture growth in OLM on various types of immobilization support, the best results were obtained with 1 cm beech wood cubes (BWCM). Enzyme activities in culture filtrate were 152 U L⁻¹ for Lac and 58 U L⁻¹ for MnP, since the chemical composition of this immobilization material induced higher Lac activity. Lower enzyme activities were obtained with polyurethane foam. Culture filtrates of OLM and BWCM were applied for dye decolorization. Remazol Brilliant Blue R (RBBR) was decolorized faster and more efficiently than Copper(II)phthalocyanine (CuP) with BWCM (80% and 60%), since Lac played a crucial role. Decolorization of CuP was initially faster than that of RBBR, due to higher MnP activities in OLM. The extent of decolorization after 14 h was 60% for both dyes.     

Equilibrium and kinetics of vancomycin adsorption on polymeric adsorbent

Isolation step of vancomycin, a glycopeptide antibiotic, is usually done from fermentation broth filtrate, while its adsorption directly from the whole broth could rationalize the process. The equilibrium and kinetics of vancomycin adsorption from broth supernatant, diluted and whole broth on polymeric adsorbent was studied in this work. Experimental equilibrium data was correlated with Sips, Langmuir, Freundlich, and linear adsorption isotherms. Agreement between measured and regressed data for the first three mentioned models did not vary much and was relatively high. The maximum adsorbed amount for supernatant was higher than for fermentation broths because mycelium particles blocked adsorbent surface. Liquid film mass transfer studies showed that external mass transfer resistance could have been neglected. Diffusion of vancomycin inside adsorbent particles was acknowledged using a nonstructural, homogenous surface diffusion and bidisperse pore models. Model simulations indicated that kinetics of the process could be improved by using smaller adsorbent particles. © 2011 American Institute of Chemical Engineers AIChE J, 2012