A systematic methodology for kinetic modeling of chemical reactions applied to n‐hexane hydroisomerization

Kinetic modeling provides chemical engineers with a unique opportunity to better understand reaction kinetics in general and the underlying chemistry in particular. How to systematically approach a modeling assignment in chemical reaction kinetics is typically less clear, especially for novices in the field. The proposed modeling methodology pursues an adequate compromise between statistical significance and physical meaning of the kinetic model and the corresponding parameters and typically results in models of an appropriate complexity. It comprises the following activities: (1) data analysis, aiming at qualitative information on the reaction mechanism and corresponding rate equations, (2) model regression to quantify this information via optimal parameter values, and (3) validation of the statistical significance and physical meaning of the parameter estimates. This methodology is successfully applied to n‐hexane hydroisomerization on a bifunctional catalyst. © 2014 American Institute of Chemical Engineers AIChE J, 61: 880–892, 2015     

Hydrodynamic characteristics of gas–solid fluidization at high temperature

Effect of temperature on the hydrodynamics of bubbling gas–solid fluidized beds was investigated in this work. Experiments were carried out at different temperatures ranged of 25–600°C and different superficial gas velocities in the range of 0.17–0.78 m/s with sand particles. The time‐position trajectory of particles was obtained by the radioactive particle tracking technique at elevated temperature. These data were used for determination of some hydrodynamic parameters (mean velocity of upward and downward‐moving particles, jump frequency, cycle frequency, and axial/radial diffusivities) which are representative to solids mixing through the bed. It was shown that solids mixing and diffusivity of particles increases by increasing temperature up to around 300°C. However, these parameters decrease by further increasing the temperature to higher than 300°C. This could be attributed to the properties of bubble and emulsion phases. Results of this study indicated that the bubbles grow up to a maximum diameter by increasing the temperature up to 300°C, after which the bubbles become smaller. The results showed that due to the wall effect, there is no significant change in the mean velocity of downward‐moving clusters. In order to explain these trends, surface tension of emulsion between the rising bubble and the emulsion phase was introduced and evaluated in the bubbling fluidized bed. The results showed that surface tension between bubble and emulsion is increased by increasing temperature up to 300°C, however, after that it acts in oppositely.     

Rotating fluidized bed with a static geometry: Guidelines for design and operating conditions

Computational fluid dynamics (CFD) simulations of the hydrodynamic behavior of rotating fluidized beds in static geometry (RFB-SG) are carried out for gas–solid flows. The rotating motion of the reactor bed is induced by the tangential injection of the gas along the circumference of the fluidization chamber. Steep gradients in the gas velocity fields both in radial and tangential direction generate turbulence. The radial and tangential drag forces fluidize the particle bed in both radial and tangential direction.An Eulerian two-fluid model is used. Gas phase turbulence is accounted for by a k–ε model adapted for rotational flows. The RFB-SG simulations provide guidelines for a design and operation with a high efficiency in gas–solid momentum transfer, excellent gas–solid separation and limited solids losses. Hydrodynamic variables like the centrifugal force, the injection pressure, the radial and tangential slip velocities, solids hold-up are calculated for both polymer particles (300 μm, 950 kg/m³, Geldart Group B) and glass beads (70 μm, 2500 kg/m³, Geldart Group A) to allow for a comparison among different fluidization chamber designs. Unstable bed behavior, like slugging and channeling, is also numerically predicted.     

Geochemical controls on the production and distribution of methylmercury in near-shore marine sediments

We examined temporal differences in sedimentary production of monomethylmercury (MMHg) at three sites in Long Island Sound (LIS). Sediment-phase concentrations of Hg species decreased from west to east in LIS surface sediments, following the trend of organic matter. However, Hg methylation potentials, measured by incubation with an isotopic tracer (200Hg), increased from west to east. 200Hg methylation potentials were enhanced in August relative to March and June, attributable to differences in activity of sulfate-reducing bacteria. Organic matter and acid-volatile sulfide influenced the distribution coefficient (KD) of inorganic Hg (Hg(II) = total Hg - MMHg) and inhibited 200Hg methylation in surface sediments. 200Hg methylation varied inversely with the KD of Hg(II) and positively with the concentration of Hg(II), mostly as HgS0, in LIS pore waters. Accordingly, we posit that a principal control on MMHg production in low-sulfide, coastal marine sediments is partitioning of Hg(II) between particle and dissolved phases, which regulates availability of Hg substrate to methylating bacteria. Most of the partitioning in LIS sediments is due to Hg-organic associations. This suggests that reductions in the organic content of coastal sediment, a potential result of nutrient abatement programs intended to inhibit eutrophication of near-shore waters, could enhance MMHg production by increasing the bioavailability of the large reservoir of "legacy Hg" buried within the sediment.     

Statistical Evaluation of Real-Time PCR Protocols Applied to Quantify Genetically Modified Maize

Real-time PCR (RTi-PCR) is the technique of choice for event-specific quantification of genetically modified organisms (GMOs) by determining the amount of event with respect to a species-specific reference gene. Reference genes can be amplified from the genome extracted from Certified Reference Materials (CRMs) or from ad hoc designed plasmids. In the present study, we statistically evaluate the performance of RTi-PCR protocols for GM maize MON810 event by using both genomic DNA from conventional CRMs and a plasmid containing sequences representative of four maize species-specific reference genes. The significance of simple and interaction effects of several variables included in the experimental design on DNA quantification methods and RTi-PCR were evaluated and discussed. Statistically significant differences on Ct values may have an impact on the GMOs quantification and consequently on the compliance of GM quantification-established legal thresholds. Our results confirm the reliability of the plasmid as alternative calibrant for the calculation of GMOs copy number.     

Quantifying Thermal Spray Coating Architecture by Stereological Protocols: Part I. A Historical Perspective

This article presents, from a historical perspective, some stereological protocols of the first order. Such protocols can be implemented to quantify statistically the architecture of thermal spray coatings and their relevant features (pores, lamellas, etc.). A forthcoming Part II of this article will address some key points to implement, from a practical point of view, such protocols.

Modélisation Mathématique de la Décantation de la Boue Rouge

A good performance of the solid‐liquid unit operation is required for the economical exploitation of the Bayer process. A computational fluid dynamics (CFD) model simulating the operation of the last washing stage mud thickener of a large Canadian alumina plant is presented. The parametric study of the impact of changes in four parameters shows that the diameter of flocculated red mud particles, the feed flow rate and the radius of the feed well are critical parameters for the operation of the thickener.     

Influence of chemical composition on mechanical properties of spark plasma sintered boron carbide monoliths

Fully dense boron carbide monoliths exhibiting fine microstructure (i.e., submicrometric grain size) are sintered by Spark Plasma Sintering. Two different commercial powder batches, exhibiting different stoichiometries (i.e., B/C ratio and oxygen content) and various amounts of secondary phases (i.e., boric acid and free carbon), are used. Their chemical composition is well‐defined by coupling different methods (Transmission Electron Microscopy associated with XRD analyses, and Instrumental Gas Analysis), and are correlated with their mechanical properties, characterized from meso‐ to macro‐scopic scales by nano‐indentation and ultrasonic pulse echography. The presence of secondary phases (graphite and boric acid) is evidenced in various proportions in each powder batch. If the boric acid disappears during sintering, the graphite remains. However, for the considered amounts of graphite (lower than 1 wt%), the low variations in graphite content have no significant effect on hardness and elasticity values. At the opposite, the presence of oxygen in boron carbide lattice, leading to a boron oxycarbide phase, induces a decrease in both hardness and elasticity properties.     

Synthesis of α‐Carbolines Starting from 2,3‐Dichloropyridines and Substituted Anilines

9H‐α‐Carbolines have been prepared via consecutive intermolecular Buchwald–Hartwig reaction and Pd‐catalyzed intramolecular direct arylation from commercially available 2,3‐dichloropyridines and substituted anilines. The combination of a high reaction temperature (180 °C) and the use of DBU were found to be crucial for the intramolecular direct arylation reactions of the 3‐chloro‐N‐phenylpyridin‐2‐amines as no reaction was observed at 120 °C and 180 °C using different inorganic and other organic bases. On the other hand, nitrogen‐methylated pyridine analogues of these substrates {N‐[3‐chloro‐1‐methylpyridin‐2(1H)‐ylidene]anilines} do undergo ring closure at 120 °C, with K₃PO₄ as base, affording the respective 1‐methyl‐1H‐α‐carbolines in good yields.     

Development of the First Oral Bioprecursors of Bis‐alkylguanidine Antimalarial Drugs

Plasmodium falciparum is responsible of the most severe form of malaria, and new targets and novel chemotherapeutic scaffolds are needed to fight emerging multidrug‐resistant strains of this parasite. Bis‐alkylguanidines have been designed to mimic choline, resulting in the inhibition of plasmodial de novo phosphatidylcholine biosynthesis. Despite potent in vitro antiplasmodial and in vivo antimalarial activities, a major drawback of these compounds for further clinical development is their low oral bioavailability. To solve this issue, various modulations were performed on bis‐alkylguanidines. The introduction of N‐disubstituents on the guanidino motif improved both in vitro and in vivo activities. On the other hand, in vivo pharmacological evaluation in a mouse model showed that the N‐hydroxylated derivatives constitute the first oral bioprecursors in bis‐alkylguanidine series. This study paves the way for bis‐alkylguanidine‐based oral antimalarial agents targeting plasmodial phospholipid metabolism.