Discrete element simulation of the dynamics of adsorbents in a radial flow reactor used for gas prepurification

Radial flow reactors (RFR) are used in thermal swing adsorption (TSA) processes for gas prepurification. The aim of this work is to show the validity of the discrete element method (DEM) to simulate the effect of thermal expansion and contraction cycles occurring in such processes on the packed bed of RFR reactors. Both mono-layered and bi-layered packed beds of adsorbents are investigated. A DEM-based model of a full-scale size unit was developed, the parameters of which were calibrated by means of particle-scale experimental measurements and simple auxiliary DEM simulations. The DEM-based model used is isothermal and the thermal expansion and contraction phenomena are modelled through the displacement of the inner and outer walls of the computational domain. First, the accuracy of this model is assessed using analytical values of the static wall pressure (i.e. with no wall motion) as well as experimental measurements of the dynamic wall pressure (i.e. with wall motion) of a bi-layered bed. Next, simulation results for a few process cycles in the case of a bi-layered packed bed indicates that little mixing occurs at the interface between the two types of adsorbents. To our knowledge, this is the first time that simulation is used to investigate the behavior of the packed bed of a RFR in a TSA process. The results obtained with the proposed model show that the DEM is a valuable tool for the investigation of such slow dynamical processes, provided a careful calibration is done.     

Claisen rearrangement of aliphatic allyl vinyl ethers in the presence of copper(II) bisoxazoline

The Claisen rearrangement of 1-methyl-2-isopropyoxycarbonyl-6-propyl allyl vinyl ether catalyzed by copper(II) bisoxazoline (Cu-box) has been investigated using density functional theory. Both the phenyl- and tert-butyl-substituted Cu-box systems have been studied. Three different reaction media (vacuum, CH2Cl2, CH3CN) have been considered. In vacuum, the phenyl Cu-box catalyzed reaction yields a (1R,6R) configured major product with a low selectivity. The solvent induces a higher selectivity and a reversal of the absolute configuration (1S,6S). However, the tert-butyl Cu-box catalyzed reaction yields (1R,6R) as the major product both in the gas phase and in the solvent with a good selectivity. Although chair-like TSs are lower in energy than boat-like TSs, the energy difference is small. This is because in the presence of the catalyst the distance between the allyl and vinyl parts of the substrate is relatively large, and thus the steric repulsion between them is smaller than would normally be expected for boat-like structures. The enantioselectivity of tert-butyl Cu-box originates from the steric interactions between the substrate and the catalyst, which are less important for the phenyl Cu-box where the enantioselectivity is determined by the solvent effects.     

Effect of surface modification on magnetization of iron oxide nanoparticle colloids

Magnetic iron oxide nanoparticles have numerous applications in the biomedical field, some more mature, such as contrast agents in magnetic resonance imaging (MRI), and some emerging, such as heating agents in hyperthermia for cancer therapy. In all of these applications, the magnetic particles are coated with surfactants and polymers to enhance biocompatibility, prevent agglomeration, and add functionality. However, the coatings may interact with the surface atoms of the magnetic core and form a magnetically disordered layer, reducing the total amount of the magnetic phase, which is the key parameter in many applications. In the current study, amine and carboxyl functionalized and bare iron oxide nanoparticles, all suspended in water, were purchased and characterized. The presence of the coatings in commercial samples was verified with X-ray photoelectron spectroscopy (XPS). The class of iron oxide (magnetite) was verified via Raman spectroscopy and X-ray diffraction. In addition to these, in-house prepared iron oxide nanoparticles coated with oleic acid and suspended in heptane and hexane were also investigated. The saturation magnetization obtained from vibrating sample magnetometry (VSM) measurements was used to determine the effective concentration of magnetic phase in all samples. The Tiron chelation test was then utilized to check the real concentration of the iron oxide in the suspension. The difference between the concentration results from VSM and the Tiron test confirmed the reduction of magnetic phase of magnetic core in the presence of coatings and different suspension media. For the biocompatible coatings, the largest reduction was experienced by amine particles, where the ratio of the effective weight of magnetic phase reported to the real weight was 0.5. Carboxyl-coated samples experienced smaller reduction with a ratio of 0.64. Uncoated sample also exhibits a reduction with a ratio of 0.6. Oleic acid covered samples show a solvent-depended reduction with a ratio of 0.5 in heptane and 0.4 in hexane. The corresponding effective thickness of the nonmagnetic layer between magnetic core and surface coating was calculated by fitting experimentally measured magnetization to the modified Langevin equation.     

Theoretical study on the structures and stabilities of silacyclopropylidenoids

Isomeric structures, energies, and properties of silacyclopropylidenoids, C₂H₄SiMX (where M?=?Li or Na and X?=?F, Cl or Br), were studied ab initio at the HF and MP2 levels of theory using the 6-31+G(d,p) and aug-cc-pVTZ basis sets. The calculations indicate that each of C₂H₄SiMXs has three stationary structures: silacyclopropylidenoid (S), tetrahedral (T), and inverted (I). All of the silacyclopropylidenoid (S) forms are energetically more stable than others except that S-LiF is by only 0.7?kcal/mol higher in energy than I-LiF. In contrast, all of the tetrahedral (T) forms are the most unstable ones except for T-NaF. Energy differences between S, T, and I forms range from 0.70 to 8.70?kcal?mol^?1 at the MP2/6-31+G(d,p) level. In addition, the molecular electrostatic potential maps, natural bond orbitals, and frontier molecular orbitals were calculated at the MP2/6-31+G(d,p) level.     

Contour approximation of data: A duality theory

Given a dataset D partitioned in clusters, the joint distance function (JDF) J(x) at any point x is the harmonic mean of the distances between x and the cluster centers. The JDF is a continuous function, capturing the data points in its lower level sets (a property called contour approximation), and is a useful concept in probabilistic clustering and data analysis. In particular, contour approximation allows a compact representation of the data: for a dataset in Rⁿ with N points organized in K clusters, the JDF requires K centers and covariances (if Mahalanobis distances are used), for a total of Kn(n+3)/2 parameters, and a considerable reduction of storage if N?K,n. The JDF of the whole dataset, J(D)?∑{J(x):x∈D}, is a measure of the classifiability of the data, and can be used to determine the “right” number of clusters for D. A duality theory for the JDF J(D) is given, in analogy with Kuhn’s geometric duality theory for the Fermat-Weber location problem. The JDF J(D) is the optimal value of a primal problem (P), for which a dual problem (D) is given, with a sharp lower bound on J(D).     

Modified estimators for the change point in hazard function

We propose the consistent estimators for the change point in hazard function by improving the estimators in [A.P. Basu, J.K. Ghosh, S.N. Joshi, On estimating change point in a failure rate, in: S.S. Gupta, J.O. Berger (Eds.), Statistical Decision Theory and Related Topics IV, vol. 2, Springer-Verlag, 1988, pp. 239–252] and [H.T. Nguyen, G.S. Rogers, E.A. Walker, Estimation in change point hazard rate model, Biometrika 71 (1984) 299–304]. By a simulation study, we show that the proposed estimators are more efficient than the original estimators in many cases.     

复合氟化物中铕(II)f-f 跃迁发射的判据及其运用

建立了Eu^2^+离子f→f跃迁发射产生的判据运用这-判据预测, 设计并合成了近四十种掺Eu^2^+的复合氟化物, 在这些基质中均观察到Eu^2^+的f-f跃迁尖峰发射。本文对所提供的判据从化学键性质和晶场效应方面作了简要解析, 并对判据的运用条件作了讨论。     

A Zwitterionic Tetrastanna(II) Cyclic Crown

A 12-membered zwitterionic tetrastanna(II) cycle 1 having a crown ether-like topology has been isolated from the deprotonation of 1,1′-methylenediimidazole ( B ) with two equivalents of Sn[N(SiMe₃)₂]₂ ( A ). The solid-state structure and NMR analysis confirms the tetrastanna(II) cycle 1 to be comprised of two stannate(II) and two stannyliumylidene ion pairs in alternating positions of the heterocycle. Computational analysis shows greater nucleophilicity at the proximally located stannate(II) centers. Nonetheless, the tetrastanna(II) cycle 1 remains poorly reactive due to engagement of Sn^II lone pair electrons in intramolecular donor-acceptor interactions. Simple deprotonation reaction between Sn[N(SiMe₃)₂]₂ ( A ) and N-(diisopropylphenyl)imidazole ( C ) in equimolar ratio has led to a stannylene 2 , involving the formation of a Sn−C covalent bond with the anionic imidazol-2-yl carbon center along with the release of NH(SiMe₃)₂. Compound 2 exists as a dimer, where the unsubstituted ring nitrogen atom coordinated intermolecularly to the other stannylene center.     

Equiatomic binary phases of Copper-Rare Earth Elements. An overview of monocuprides from first-principles calculations

Equiatomic binary phases of copper with rare earth (RE) elements exhibit either primitive cubic ( ) or orthorhombic (Pnma) structures and in some cases both. By using density functional theory (DFT), we calculated the enthalpies of formation along the series of RE elements combined equimolarly with copper. For RE from Sc to Lu, the calculated enthalpies of formation fall in the range −49.8 kJ/mol for LuCu to −9.1 kJ/mol for the least thermodynamically stable CeCu. Except NdCu, all the other cubic or orthorhombic compounds exhibit lattice stability. Either forms of NdCu indicated lattice instability. Along the Sc-group, the hypothetical primitive cubic and orthorhombic forms of LuCu are found thermodynamically and mechanically stable. The overall trend of the formation enthalpies as a function of the Meyer Periodic Number is consistent with the energy trend of the 4 f-orbital filling as moving from Sc to Lu monocuprides. In addition, the calculated Gibbs free energies indicate that the thermodynamic stability is largely due to the entropic contributions. All standard DFT calculations were also repeated with DFT+U to better describe the correlation between the 5d–4f and 3d shells of RECu compounds. It has been found that DFT+U slightly affects the enthalpies of formation of RECu binaries. Moreover, DFT+U shifts up the f-band energies of RECu with light RE elements (such as La, Ce and Pr) and in contrast lowers them in the case of RECu with heavy RE elements from Nd to Lu.