Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha I. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha has been evaluated over unsupported transition metal sulfide catalysts of the second row in the Periodic Table. The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enabled the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide (RuS₂) is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha.     

Studies on Silicon Containing Nano-hybrid Epoxy Coatings for the Protection of Corrosion and Bio-Fouling on Mild Steel

An epoxy nano-composite coating was developed using amine functionalized nZnO (in the amount of 2.5 %, 5.0 % and 7.5 wt %) as the dispersed phase and a commercially available epoxy resin as the matrix phase. The structural features of these materials were ascertained by FT-IR spectral studies. The anti-corrosive properties of the epoxy/nZnO hybrid coatings in comparison with a virgin coating were investigated by a salt spray test and electrochemical impedance spectroscopy technique. The surface morphology determined by SEM, indicates that nZnO particles were dispersed homogenously through the epoxy polymer matrix. The results showed improved antifouling and anticorrosive properties for epoxy-nZnO hybrid coatings.     

KINETICS OF URANIUM EXTRACTION BY MACROPOROUS BIFUNCTIONAL PHOSPHINIC ACID RESIN

ABSTRACT

The rate of extraction of uranium by macroporous bifunctional phosphinic acid (MPBPA) resin from nitric acid medium has been studied under particle diffusion controlled conditions. The internal diffusion coefficient was found to increase with increase in temperature and decrease with increase in particle size. The activation energies and entropies suggest that the extraction of uranium essentially follows ion exchange mechanism at low concentration of nitric acid while it is through linkage of >P=0 group of the resin at high concentrations.     

One‐Dimensional Pseudo‐Homogeneous Packed‐Bed Reactor Modeling: I. Chemical Species Equation and Effective Diffusivity

Packed‐bed reactor experimentation is a key tool used in order to formulate chemical kinetics. The chemical species equation and overall methodology are described for a one‐dimensional pseudo‐homogeneous packed‐bed reactor model useful for experimental calibration of chemical kinetics. Over the history of simulation development for this equation there exist numerous different effective diffusivity correlations. The included historical review and parametric study of these correlations help to determine the correct choice based on numerical simplicity and model outcomes. A subsequent review paper describes the energy equation and effective thermal conductivity correlations while coming to a generalized conclusion regarding modeling efforts.     

Impact of density gradients on the fluid flow inside a vibrating cavity subjected to soret effect

Computational fluid dynamics simulations of thermovibrational flows in a square cavity filled with a water–isopropanol mixture has shown that inaccurate density calculations can predict very different flow behaviours. Specifically, comparison has been made between two density calculation models, viz., a weighted‐average scheme and the Perturbed Chain Statistical Associating Fluid Theory equation of state. While the latter approach predicts a stronger flow in the cavity due to the convective instabilities that are induced by the large spatial gradients in density, the weighted‐average scheme cannot predict this since it does not explicitly depend on the temperature of the mixture. © 2012 Canadian Society for Chemical Engineering     

Contribution of organomodified clay on hybrid microstructures and properties of epoxidized natural rubber‐based nanocomposites

Influence of organic modifying agent of clay on dispersion, distribution, hybrid microstructure formation, and associated performance properties of epoxidized natural rubber‐based composites was evaluated. Binary and ternary composites of carbon black (CB) and two organomodified layered silicates (i.e., nanomer I30E and Cloisite 30B) were prepared and characterized based on small angle X‐ray scattering, transmission electron microscopy, hydrodynamic swelling, tensile measurement, and dynamic mechanical analyses. Greater extent of exfoliation and “nanounit” formation was noted in ternary composites containing nanomer I30E, which was reflected in higher interfacial roughness (d_s = 2.82) and lower radius of gyration (R_g = 205 Å). Morphological observations suggested higher nanomer I30E–CB interactions than that of Cloisite 30B–CB. The interplatelet distance in Cloisite 30B (d = 1.83 nm) stacks was lower than that of nanomer I30E (d = 2.26 nm). These two factors jointly contributed in higher breakdown of nanomer I30E stacks by CB than that of Cloisite 30B stacks. Greater exfoliation and nanounit formation in I30E–CB‐filled nanocomposite was also reflected in increased degree of crosslinking (n = 20 × 10^?5%), tensile modulus/strength, half height width of damping peak (20.3°C), and filler effectiveness (C = 0.33). POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Review of Chemical Reactions in the NO Reduction by CO on Rhodium/Alumina Catalysts

The emissions of nitric oxide and carbon monoxide from internal combustion engines are of primary concern due to their impact on the environment and people's health. Since rhodium has proven to be an important catalyst for the reduction of nitric oxide by carbon monoxide, its accurate modeling is of significant value to industry. This paper reviews the literature with respect to this interaction in order to explain the history of the detailed reactions occurring on the surface. This review was accomplished in the absence of other species in order to focus the efforts and reduce the complexity of the task. In addition, this work presents an appropriate global reaction expression based on these detailed reactions for use in one-dimensional aftertreatment catalyst models.     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

Phase Constitution During Sintering of Red Mud and Red Mud–Fly Ash Mixtures

The phase constitution during the sintering of pure red mud and red mud–fly ash mixtures was studied in the temperature range of 900°–1250°C. The phases formed at different sintering temperatures were analyzed by X-ray powder diffraction. The phases that are likely to form at equilibrium at any isotherm were predicted using the Gibbs free energy minimization technique and the databases provided in the FactSage software. Although the thermodynamic prediction is in reasonable agreement with the experimental results for the major phases, there is some disagreement regarding the minor phases, especially the more complex phases. The major limitation of the thermodynamic approach presently is the non-availability of thermodynamic data for several complex and multi-component solution phases.