Role of rare earth cations in Y zeolite for hydrocarbon cracking

Reaction kinetics data were collected for isobutane conversion over a series of ultra stable Y (USY) zeolite catalysts with and without rare earth cations and subjected to various extents of dealumination by steaming. We conducted these reaction studies at low temperatures (523-573 K) using isobutane feed streams containing known levels of isobutylene (100-400 ppm) so that the kinetics were controlled by bimolecular hydride transfer and oligomerization/beta-scission processes with little or no participation of monomolecular initiation reactions. These experimental conditions led to stable catalyst performance with the main products of isobutane conversion being propane, n-butane, and isopentane, with smaller amounts of propylene, trans-2-butene, and cis-2-butene. The rates of formation of these products per Br?nsted acid site (as counted by pyridine adsorption) depended exponentially on Br?nsted acid site density, regardless of whether the catalyst contained rare earth cations. Kinetic modeling showed an exponential dependence of hydride transfer and oligomerization/ beta-scission reaction rates on Br?nsted acid site density which translated into composite activation energies for these reactions having a linear relationship with site density. Based on results in the literature from theoretical calculations, we suggest that increasing Br?nsted acid site density in zeolite Y leads to larger zeolite elasticity, increased stabilization of cationic transition states, and lower composite activation barriers for hydride transfer and beta-scission steps. The role of rare earth cations, therefore, is to ensure the retention of high Br?nsted acid site density under hydrothermal conditions, such as in fluid catalytic cracking (FCC) regenerators, where steam would dealuminate the Y zeolite framework and reduce this site density. It is for this reason that hydride transfer reaction rates are high in the presence of rare earth cations and lead to higher yields of less olefinic gasoline during FCC.     

Estimation of thermal conductivity of ethylene glycol-based nanofluid with hybrid suspensions of SWCNT–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by correlation and ANN methods using experimental data

In the present paper, the effects of temperature and volume fraction on thermal conductivity of SWCNT–Al₂O₃/EG hybrid nanofluid are investigated. Single-walled carbon nanotube with outer diameter of 1–2 nm and aluminum oxide nanoparticles with mean diameter of 20 nm with the ratio of 30 and 70%, respectively, were dispersed in the base fluid. The measurements were conducted on samples with volume fractions of 0.04, 0.08, 0.15, 0.3, 0.5, 0.8, 1.5 and 2.5. In order to investigate the effects of temperature on thermal conductivity of the nanofluid, this characteristic was measured in five different temperatures of 30, 35, 40, 45 and 50 °C. The results indicate that enhancement of nanoparticles’ thickness in low volume fractions and at any temperature causes a considerable increment in thermal conductivity of the nanofluid. In this study, the highest enhancement of thermal conductivity was 41.2% which was achieved at the temperature of 50 °C and volume fraction of 2.5%. Based on the experimental data, an experimental correlation and a neural network are presented and for thermal conductivity of the nanofluid in terms of volume fraction and temperature. Comparing outputs of the experimental correlation and the designed artificial neural network with experimental data, the maximum error values for the experimental correlation and the artificial neural network were, respectively, 2.6 and 1.94% which indicate the excellent accuracy of both methods in prediction of thermal conductivity.     

First principle study of unzipped boron nitride nanotubes

Systematic first principle calculations have been used to explain the dangling bonds behaviour in the rolling up of a boron nitride nanoribbon (BNNR) to construct a single-walled boron nitride nanotube (BNNT). We found in armchair BNNR two degenerate dangling bonds split and move up to higher energies due to symmetry breaking of system. While in zigzag BNNR changing the topology of system does not affect on metallic features of the band structure, but in unzipped BNNT case a metallic-semimetallic phase transition occurs. Considering the width dependent electronic properties of hydrogen passivated armchair BNNRs, exhibit zigzag behaviour of energy gap in agreement with previous results.     

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.     

Structural and electronic properties of boron-doped double-walled silicon carbide nanotubes

The effects of boron doping on the structural and electronic properties of (6,0)@(14,0) double-walled silicon carbide nanotube (DWSiCNT) are investigated by using spin-polarized density functional theory. It is found that boron atom could be more easily doped in the inner tube. Our calculations indicate that a Si site is favorable for B under C-rich condition and a C site is favorable under Si-rich condition. Additionally, B-substitution at either single carbon or silicon atom site in DWSiCNT could induce spontaneous magnetization.     

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

A polymer‐anchored ruthenium(II) catalyst was synthesized and characterized. Its catalytic activity was evaluated for the preparation of primary amides from aqueous hydration of nitriles in neutral condition. A range of nitriles were successfully converted to their corresponding amides in good to excellent yields. The catalyst was also effective in the preparation of secondary amides from the coupling of alcohols and amines. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity. Copyright © 2014 John Wiley & Sons, Ltd.     

On Monomial Reduction and Polynomial Expressions with Respect to Binomial Ideals

Let I ? K[x ₁,…, x _n ] be an ideal and G be the reduced Gröbner basis of I with respect to lexicographic monomial order. We introduce the index of an expression of f ∈ K[x ₁,…, x _n ] with respect to G. A minimal expression is characterized as the one with zero G-index. In case where I is a binomial prime ideal, a new division algorithm with minimal and unique expression is presented. The application of our new method on benchmark polynomial systems cyclic-9 and cyclic-12 shows its superiority in comparison with the existing division algorithm.     

Garnets with dodecahedral rare earths and scandium,octahedral scandium,and tetrahedral iron. I. Compositional and structural studies

It has been found possible to prepare garnets with magnetic trivalent rare-earth ions filling all or most dodecahedral sites while nonmagnetic Sc³⁺ ions fill all octahedral sites and magnetic Fe³⁺ ions fill all or most tetrahedral sites. Phase-pure garnets found include {RE_3?ySc_y}[Sc₂](Fe₃)O₁₂, where RE is Sm, Eu, Gd, Tb, or Dy, and y can be zero with Sm and Eu; {Nd₃}[Sc₂](Fe_zGa_3?z)O₁₂; and other NdScFe garnets with small amounts of Y, Gd, or Lu added in order to bring z up to 3. Results are interpreted in terms of “size factor” and “comfort factor.”     

Addressing first derivative discontinuities in orbital-optimised opposite-spin scaled second-order perturbation theory with regularisation

ABSTRACT

Orbital-optimised opposite-spin scaled second-order perturbation theory (O2) generates a single-reference wave function composed of approximate Brueckner orbitals with fourth-order computational scaling. While O2 provides significantly improved treatment of radicals by reducing spin contamination, it has been shown to suffer from first derivative discontinuities for bond stretching near the unrestriction point. That qualitative failure is resolved in this work by the implementation of regularised O2, which includes a regularisation parameter in the denominator of its second-order term. The value of the regularisation parameter is semi-empirically chosen to qualitatively describe bond stretching energetics of hydrogen, ethane and ethene, while also considering the effect of the regularisation parameter on thermochemical errors for the well-known Gaussian-2 (G2) test set. The generality of the empirical scaling and semi-empirical regularisation parameter is studied by application to the 3dMLBE20, DBH24, RSE43 and W4-11 test sets. We demonstrate that accuracy of O2 is roughly maintained and sometimes even improved by regularisation, with root mean squares of regularised O2 between factors of 1.6 and 0.8 from corresponding root mean squares of O2.