Numerical simulation of fixed-bed catalytic reactor for isopropyl alcohol synthesis

The mathematical model and the method of its numerical analysis for fixed-bed catalytic reactors were developed and were applied to the pilot reactor of isopropyl alcohol (IPA). The experimental results from pilot test runs were used to test and verify the simulation results. The numerical simulation gives the IPA concentration and temperature profiles in the reactor. The production of IPA from a commercialized ethanol rector was examined. The operation conditions of IPA synthesis were established.     

Migration of Intergranular Liquid Films and Formation of Core-Shell Grains in Sintered TiC–Ni Bonded to WC–Ni

When TiC–20 wt% Ni powder mixtures are sintered at 1400°C, relatively large TiC grains possibly containing some Ni form with near-equilibrium shapes. When these specimens are heat-treated again at 1400°C in contact with sintered WC–20 wt% Ni pieces, the liquid films between the TiC grains in the contact region migrate against their increasing curvatures, forming (Ti,W)C solid solution behind them. These migrating liquid films reverse their directions on further heat-treatment. As in other alloys, this liquid film migration must be driven by the coherency strain energy produced by W diffusion at the surface of the dissolving TiC grains. Shells of (Ti,W)C solid solution also form around the cores of TiC grains near the contact region, and this process is probably driven by both coherency strain energy and free energy of mixing. At some contact regions, (Ti,W)C precipitates nucleate and grow, probably driven mainly by the free energy of mixing. In powder mixtures, the formation of core-shell grains is expected to be driven by the coherency strain energy, the free energy of mixing, and the capillary effect.     

Effect of clinoptilolite addition and solids retention time on the extracellular polymeric substances composition and soluble chemical oxygen demands in activated sludge

This study was carried out to compare EPS (Extracellular Polymeric Substances) composition between conventional activated sludge (AS) and activated sludge dosed with clinoptilolite (CAS). Additionally, those were compared with organic removal efficiency in the effluent in conjunction with EPS concentrations. The experiments were conducted at SRT (Solids Retention Time) ranging from 5 to 100 d. For the CAS, proteins were more readily observed for SRT 20 and 100 d compared to that of the AS. Polysaccharide concentration in the sludge was greatly increased for the CAS, but it was significantly diminished when the SRT was extended. The level of EPS concentration observed from the effluent had the same pattern of variation for the two different types of systems. Regardless of type of reactor, the ratio of proteins for sludge versus effluent was independent of SRT, but the ratio of polysaccharides diminished as SRT increased. In the long run, the degree of protein synthesis directly ascribed to concurrent enhancement of SCOD removal efficiency was slightly more in the CAS. It was decided that clinoptilolite added system could be more reliably retrofitted to a conventional activated sludge process.     

Preparation of stable polyurethane-polystyrene copolymer emulsions via RAFT polymerization process

Stable polyurethane-polystyrene (PU-PS) copolymer emulsions were prepared by the polymerization of 2-hydroxyethyl acrylate (HEA)-capped PU macromonomer and styrene, using azobis(isobutyronitrile) (AIBN), a radical initiator, and 4-((benzodithioyl)methyl)benzoic acid, a reversible addition-fragmentation chain transfer (RAFT) agent. As the molar ratio of the RAFT agent to AIBN increased, the zeta potential of the resulting copolymer emulsion increased, but the average size and size distribution of the emulsion droplets decreased. A living polymerization of HEA end-capped PU macromonomer and styrene was characterized by a linear increase in the molecular weight and decrease in the molecular weight distribution with consumption of monomers. The tensile strength, hardness and water-resistance of the copolymer films, prepared from the PU-PS copolymer emulsions, were much greater than those of the films prepared from the pure PU emulsion. The copolymer emulsions, prepared via the RAFT polymerization process, are expected to exhibit better storage stability than those prepared via the conventional free radical polymerization process, due to the presence of carboxyl groups derived from the RAFT agent at the PS block termini.     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

Microstructural Evidence for Diffusion-Driven Tetragonal-to-Orthorhombic Phase Transformation in Y-Ba-Cu-O Superconductor

Microstructures of Y-Ba-Cu-O superconductor were observed using a polarized microscope. Orthorhombic and tetragonal phases were easily distinguished by the optical etching with cross-polarized light. In the specimen cooled rapidly in oxygen, it was possible to see the path of oxygen diffusion by observing the variation of the twin concentration. At the boundary between transformed and untransformed materials, evidence for diffusion-driven transformation could be clearly seen.     

Reynolds number scaling of flow in a Rushton turbine stirred tank. Part I—Mean flow, circular jet and tip vortex scaling

We consider scaling of flow within a stirred tank with increasing Reynolds number. Experimental results obtained from two different tanks of diameter 152.5 and 292.1 mm, with a Rushton turbine operating at a wide range of rotational speeds stirring the fluid, are considered. The Reynolds number ranges from 4000 to about 78,000. Phase-locked stereoscopic PIV measurements on three different vertical planes close to the impeller give phase-averaged mean flow on a cylindrical surface around the impeller. The scaling of θ- and plane-averaged radial, circumferential and axial mean velocity components is first explored. A theoretical model for the impeller-induced flow is used to extract the strength and size of the three dominant elements of the mean flow, namely the circumferential flow, the jet flow and the pairs of tip vortices. The scaling of these parameters with Reynolds number for the two different tanks is then obtained. The plane-averaged mean velocity scales with the blade tip velocity above a Reynolds number of about 15,000. However, parameters associated with the jet and tip vortices do not become Reynolds number independence until Re exceeds about 10⁵. The results for the two tanks exhibit similar Reynolds number dependence, however, a perfect collapse is not observed, suggesting a sensitive dependence of the mean flow to the finer details of the impeller.     

CO hydrogenation over potassium-promoted Fe/carbon catalysts

The effects of potassium on the catalytic behavior in CO hydrogenation over K-promoted Fe/carbon catalysts having low K/Fe ratios were investigated. Even though the doses of potassium were low the promotional effects were pronounced, especially on the olefin-to-paraffin ratio, and theC ₃ toC ₄ olefin selectivities of the K-promoted catalysts were as high as 51 to 66 mol%. Over the catalysts having no or low potassium content the olefin-to-paraffin ratio and the ratio of the CO₂ formation rate to the rate of CO conversion to hydrocarbons remained roughly the same regardless of temperature, while over the K-promoted catalysts having higher potassium content they increased with temperature. Formation of significant amounts of filamentous carbon was observed in the K-promoted catalysts; however, the carbon deposition did not appear to affect the inherent activity and selectivity of the K-promoted catalysts.     

Adhesion property of novel polyimides with 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride

Novel polyimides were synthesized from 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride (6FPPMDA) by a conventional two‐step process: the preparation of poly(amic acid) followed by solution imidization via refluxing in p‐chlorophenol. The diamines used for polyimide synthesis included bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, bis(3‐aminophenyl)‐4‐trifluoromethylphenyl phosphine oxide, and bis(3‐aminophenyl)phenyl phosphine oxide. The synthesized polyimides were designed to have a molecular weight of 20,000 g/mol by off‐stoichiometry and were characterized by Fourier transform infrared, NMR, differential scanning calorimetry, and thermogravimetric analysis. In addition, their intrinsic viscosity, solubility, water absorption, and coefficient of thermal expansion (CTE) were also measured. The adhesion properties of the polyimides were evaluated via a T‐peel test with bare and silane/Cr‐coated Cu foils, and the failure surfaces were investigated with scanning electron microscopy. The 6FPPMDA‐based polyimides exhibited high glass‐transition temperatures (280–299°C), good thermal stability (>530°C in air), low water absorption (1.46–2.16 wt %), and fairly low CTEs (32–40 ppm/°C), in addition to good adhesion properties (83–88 g/mm) with silane/Cr‐coated Cu foils. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1801–1809, 2005     

Electrochemical studies of pyrite oxidation and reduction using freshly-fractured electrodes and rotating ring-disc electrodes

Oxidation and reduction processes on coal- and mineral-pyrite surfaces have been investigated to better understand the reactions that control the hydrophobicity and flotation behavior of pyrite. The incipient oxidation and reduction reactions were studied using fresh surfaces of pyrite that were created by in situ fracturing electrodes potentiostated at a predetermined potential. Chronoamperometry immediately after fracture and subsequent cyclic voltammetry have established that fresh fracture surfaces of pyrite instantaneously assume a unique potential (referred to as the “stable” potential) at which neither oxidation nor reduction takes place. For Peruvian and Chinese pyrites, the stable potential is −0.28 V (standard hydrogen electrode, SHE) at pH 9.2 and 0 V at pH 4.6. The initial oxidation of pyrite begins at potentials slightly positive of the stable potential and is believed to produce a hydrophobic sulfur-rich species, most likely a polysulfide or metal-deficient sulfide. A rotating ring-disc electrode (RRDE) was employed to study the kinetics and mechanisms of surface reactions on pyrite over moderate potential ranges. Two distinct soluble reduction products (ferrous hydroxide and HS⁻) and one distinct soluble oxidation product (ferrous hydroxide) were observed on pyrite in alkaline solutions. It is concluded that the initial oxidation of pyrite and the oxidation of ferrous to ferric hydroxide occur in a similar potential range. When the electrode is oxidized, e.g. by polishing, prior to experiments, the initial oxidation of pyrite is masked by the oxidation of ferrous hydroxide, making it difficult to study the oxidation of pyrite itself.