Coking kinetics of a Cr2O3/Al2O3 catalyst during 1-butene dehydrogenation: Effect of H2 partial pressure

The influence has been studied of the partial pressure of hydrogen (0–30 kPa) upon the coking rate of a Cr₂O₃/Al₂O₃ commercial catalyst during 1-butene dehydrogenation. Coke deposition has been analysed using a monolayer-multilayer reversible coke growth model (MMRC model). This model provides good fits to the experimental data, within the range of partial pressure of H₂ studied, and allows us to estimate the main kinetic parameters involved in the coking-deactivation process. The results obtained reveal a dual effect of hydrogen: competition against 1-butene for the active sites and the removal of coke precursors from the catalyst surface. Bom effects diminish the coking rate as the H₂ partial pressure is increased.     

A SIMPLE METHOD FOR STUDYING THE KINETICS OF GAS-SOLID REACTIONS IN A FLUIDIZED BED REACTOR

A methodology for studying the kinetics of gas-solid reactions in a fluidized bed reactor is presented. This procedure is based on the analysis of the response of the system (flue gases) when batches of solids of different weight are added to the reactor. The method has been applied to the study of limestone particle calcination. The calcination rate constants obtained are in good agreement with those found in the literature. The method offers the advantage of simplicity and avoids the use of model assumptions or empirical correlations.     

Homogeneous Catalyzed Ozone Decomposition in the Presence of Co(II).

The homogeneous decomposition of ozone in the presence of a Co(II) catalyst has been investigated in aqueous solution. Under the conditions investigated (Co(II) concentration: 0.0 – 2.0?ppm, pH: 1.6- 8.4, O₃ concentration: 5 10^?5 – 2.0 10⁴?M) the process can be assumed to follow pseudo first order kinetics with respect to ozone. Cobalt concentration dependency also obeys first order kinetics although it may be considered to reach a steady state concentration. pH exerts a positive influence on the decomposition rate from 1.6 to 7.1, the process leveling off at pH 8.4. An Arrhenius analysis of the temperature effect gave a moderate activation energy of the global reaction (E=10917?cal mol^?1). A more detailed radical mechanism than a simple pseudo first order reaction can be postulated for simulation purposes. By numerical optimization of some unknown kinetic constants the influence of several operating variables can be adequately predicted.     

Stretching and deformation vibrations of CH2, C(CH3) and O(CH3) groups of poly(methyl methacrylate)

Infrared and Raman spectra of atactic PMMA and infrared spectra of stereoregular PMMA and of its four deuterated derivatives

, were measured. They were used to assign the bands of stretching and deformation vibrations of CH₂, CCH₃ and OCH₃ groups in the infrared and Raman spectra and to discuss the effect of stereoregularity on these bands in the infrared spectra.     

The potentiometric behaviour of copolymers of methacrylic acid in water-ethanol solutions

Summary The synthesis is reported of copolymers of styrene with methacrylic acid and of methyl methacrylate with methacrylic acid by radical copolymerization, of copolymers of methyl methacrylate with methacrylic acid by partial alkaline hydrolysis of poly(methyl methacrylate), and of block copolymers of styrene with methacrylic acid. Modified titration curves of all these copolymers were recorded in water and water-ethanol solutions. In a solution containing 50 mass.% ethanol, only small differences could be observed between the potentiometric behaviour of the individual copolymers and polymethacrylic acid. Also, there were no essential differences in any of the solvents used between the potentiometric behaviour of block copolymers of styrene with methacrylic acid, on the one hand, and polymethacrylic acid, on the other. On the contrary, maxima and minima were always observed on the modified titration curves of statistical copolymers with a higher content of the hydrophobic comonomer in solutions with a high water content. Thus, using the modified titration curves, it is possible to decide whether a given copolymer is of the block or statistical type.     

Contribution to the hydration of expansive cement on the basis of metakaolinite

The study of hydration of expansive cement prepared from 64% portland cement clinker, 23% metakaolinite and 13% CaSO₄.2H₂O is described. It was found that in the course of a 10-day hydration period, all the gypsum entered the reaction with the formation of ettringite. In 7–10 days, after the termination of the expansion processes, typical stalk-like crystals were transformed into leaf-shaped or other formations. Ettringite was identified even after 4 months of hydration. Monosulphate (3CaO.Al₂O₃.CaSO₄.12H₂O) was found in none of the investigated high-expansion cement paste samples.     

The correlation between electrical properties and structure of substituted polyacetylenes

Summary The electrical conductivity of polyphenylacetylenes and polyhalophenylacetylenes was measured in dependence on the temperature and on the type of catalyst used for polymerization. The electrical conductivity increased with increasing temperature. The energy gap was calculated from the temperature dependence on the electrical conductivity; it decreased with increasing number of conjugated double bonds in the polymer chain and with the regularity of structure of the polymer. The number of double bonds, cyclization and configurations were determined by ¹H and ¹³C-NMR. In polyphenylacetylenes only aliphatic carbons deriving from cyclohexadiene units were found but no such units were found in polyhalophenylacetylenes. By UV-vis measurement the number of conjugated double bonds in segments was estimated. The synthesized polymers were amorphous. Their molecular weight was between 2000 and 74.000.     

A computational fluid dynamic analysis of gas and particle flow in flame spraying

The flame spraying process, which is a common industrial thermal spraying application, has been analyzed by means of three-dimensional computational fluid dynamics (CFD) simulations. The process used at the Volvo Aero Corporation for the coating of fan and compressor housings has been modeled. The process uses the Metco 6P torch (Metco, Westbury, NY), which ejects a mixture of acetylene and oxygen at high speed through a ring of 16 orifices to form the flame. A stream of argon gas flowing through an orifice in the center of the ring carries a powder of nickel-covered bentonite through the flame to the spray substrate. The torch is cooled by a flow of air through an outer ring of 9 orifices. The simulation emulated reality closely by including the individual inlets for fuel, cooling air, and injected particles. The gas combustion was simulated as a turbulent, multicomponent chemically reacting flow. The standard, two-equation k-ε turbulence model was used. The chemical reaction rates appeared as source terms in the species transport equations. They were computed from the contributions of the Arrhenius rate expressions and the Magnussen and Hjertager eddy dissipation model. The first simulations included several intermediate chemical substances whose predicted concentration agreed favorably with measurements. Later, more simplified simulations incorporated only the global chemical reaction involving the initial and the final products, with corrections to the thermal properties being made to account for the missing intermediaries. The gas velocity and temperature fields predicted by the later simulations compared satisfactorily to those predicted by the earlier, more elaborate, ones. Therefore, the final simulations, which incorporated injected particles, were conducted employing the simplified model with only the global reaction. An in-house finite difference code was developed to calculate particle properties. Allowance was made for elliptical shapes, phase changes, and internal heat transfer with regard to the composite material. The particle velocities and temperatures predicted by the final simulations compared fairly well with experimental results obtained with the optical DPV2000 system.     

Note: The intermodulation lockin analyzer

Nonlinear systems can be probed by driving them with two or more pure tones while measuring the intermodulation products of the drive tones in the response. We describe a digital lockin analyzer which is designed explicitly for this purpose. The analyzer is implemented on a field-programmable gate array, providing speed in analysis, real-time feedback, and stability in operation. The use of the analyzer is demonstrated for intermodulation atomic force microscopy. A generalization of the intermodulation spectral technique to arbitrary drive waveforms is discussed.