Gasification of charcoal using supercritical CO2 at high pressures

A novel one-shell high temperature and high pressure semi-continuous reactor has been developed for the study of the Boudouard reaction at temperatures up to 820 °C and pressures up to 32.5 MPa. Semicontinuous gasification of charcoal using supercritical CO₂ has been achieved at conversions up to 90.8% (w/w) at LSHV between 20 and 30 h⁻¹ after 5–9 h. A gasification model is proposed and validated. Effective rates of gasification (1.32 ± 0.12) × 10⁻⁶ to (6.10 ± 2.03) × 10⁻⁵ s⁻¹ were obtained. The results indicated that this method is technically feasible for the on-line production of high pressures streams of CO/CO₂ in the lab for carrying out further chemistries, avoiding the use of CO high pressure bottles.     

A kinetic investigation into the removal of carbobenzyloxy group from protected amines via hydrogenolysis reaction

Hydrogenolysis of a carbobenzyloxy group (CBz) was studied utilizing molecular hydrogen in the presence of carbon-supported palladium catalyst. It was demonstrated that the kinetics of the reaction are greatly influenced by the presence of the CO₂ by-product. It was found out that the presence of CO₂ determines whether the reaction is first or zero order since it causes deactivation of the catalyst via inhibition. The effect of potassium carbonate (K₂CO₃) and triethylamine (TEA) as additives was investigated. A considerable solvent effect was also observed that may be explained by the variation of dispersion of the catalyst from one solvent to another.     

On-line H NMR spectroscopic investigation of hydrogen bonding in supercritical and near critical CO2–methanol up to 35 MPa and 403 K

On-line NMR spectroscopy can beneficially be applied to studies of supercritical and near-critical fluids as an alternative to optical spectroscopy. Up to now high pressure NMR experiments are predominantly accomplished using custom made NMR batch reactors. The authors present a novel high pressure cell with displacement plunger for on-line NMR experiments on compressible fluids which can be used in conjunction with commercially available SCF NMR flow probes. The on-line technique offers advantages compared to stopped flow techniques such as enhanced control of mixture composition and reaction parameters as well as the facility of engagement into the reaction. The new apparatus is used for NMR studies on hydrogen bonding of methanol in near critical and supercritical carbon dioxide up to 403 K and 35 MPa for which data on the chemical shift of the hydroxyl group and methyl group are reported and interpreted.     

Kinetic study of the deep hydrodesulfurization of dibenzothiophene over molybdenum carbide supported on a carbon black composite: Existence of two types of active sites

Hydrodesulfurization (HDS) is part of the hydrotreating process, which is an ensemble of several reactions (HDN, HDO, HDS, etc.) taking place simultaneously at the industrial scale. Only sulfur is currently submitted to drastic Europeans specifications and conventional commercial catalysts cannot reach the specifications at low cost. This paper presents the behavior of a potential substitute catalyst tested for the deep HDS of a model molecule such as the dibenzothiophene (DBT). The substitute is molybdenum carbide supported on a mesoporous carbon black composite of surface area 240 m² g⁻¹. A global kinetic study of the deep HDS of DBT (300 ppm S) was performed at 623 K and 5.0 MPa and a global kinetic model was proposed as well as global rate constants were calculated to obtain theoretical plots of concentration versus contact time to compare with the experimental data. The kinetic model and global kinetic orders were confirmed as an acceptable correlation was found between calculated and experimental data. Furthermore, the determination of the global kinetic orders indicated that two types of active sites must be present on the surface in order to explain the observed results.     

Electrochemical impedance spectroscopy of a free-standing oxide film

The corrosion of low carbon steel in natural sea-water is characterized by the formation and growth of compact and thick layers composed of oxides, insoluble salts and organic materials. These layers are the result of corrosion processes induced by local environmental conditions, water oxygen supply; ionic species; bacteria and organic matter. The exchange of various species (ions, molecules, gas) between sea-water and the rust layers or the metal depends both on the kinetics of the Faradaic reactions of the entities with either the oxides or the metal, as well as on their transport properties through the different strata of the rust layers. In this work, an impedance study was carried out using the 4-electrodes cell arrangement with corrosion products picked up on steel sheet piling immersed for 25 years and analyzed as free standing membranes. This new approach is a good way to reach the specific transport and transfer properties of the oxide without being blurred by the metal influence. The physical model developed in this work was based on a transmission line, and accurately described the experimental diagrams. The electronic resistivity of the oxide layer, its porosity, the mean pore size and the reaction kinetics parameters could be determined from the fittings.     

Films and fibers of oriented single wall nanotubes

As-produced nanotubes form a light, fragile and isotropic soot. Different efforts are made to process nanotubes into macroscopic forms of more practical use and more controlled properties. We briefly review in this paper two methods recently proposed to make films of magnetically aligned nanotubes and fibers by using an electrophoretic method. Preferential orientation of the nanotubes in the plane of the films or along the fiber axis is an important feature of the obtained materials. Then we describe in details a different, spinning like, process for making fibers out of single wall carbon nanotubes. This process consists of dispersing the nanotubes in a surfactant solution, re-condensing the nanotubes in the flow of a polymer solution to form a nanotube mesh, and then collating this mesh to a nanotube fiber. The behaviors of the surfactant-stabilized dispersions, which are also presented, are critical for this process. The degree of nanotubes alignment in dried fibers has been characterized by X-ray scattering. It is found to be smaller than the alignment obtained in the previous materials. However, the processing is simpler and faster and potentially scalable for large-scale production.     

未掺杂半绝缘GaAs中受主及电中性EL2分布的研究

测量了未掺杂半绝缘（ＳＩ）ＬＥＣＧａＡｓ中总的、电中性的ＥＬ２及净受主浓度分布和碳分布。结果表明，总ＥＬ２浓度径向分布呈Ｗ形而不是均匀的，净受主浓度径向分布呈∧形或∩形而不是Ｍ形。电中性ＥＬ２的Ｗ形径向分布由总ＥＬ２浓度的Ｗ形径向分布决定，而不是由于净受主的不均匀分布。有些样品中净受主浓度远大于碳浓度．意味着这些样品中除碳外还存在高浓度的其它受主。     

Single‐Walled Carbon Nanotube Dispersions in Poly(ethylene oxide)

Dispersions of single‐walled carbon nanotubes (SWNTs) in poly(ethylene oxide) (PEO) assisted by a lithium‐based anionic surfactant demonstrate an electrical percolation of 0.03 wt.‐% and a geometrical percolation, inferred from melt rheometry, of 0.09 wt.‐%. Both the melting temperature and the extent of crystallinity of the PEO crystals decrease with increasing SWNT loading. Raman spectroscopy of the nanocomposites indicates a down‐shift of the SWNT G‐modes and suggests that the nanotubes are subjected to tensile stress transfer from the polymer at room temperature.     

X-ray structure analysis and elastic properties of a fabric reinforced carbon/carbon composite

The effect of heat treatment on microstructure of a plain-weave carbon fabric reinforced carbon-carbon composite with phenolformaldehyde-derived carbon matrix was investigated by X-ray diffraction. The diffraction patterns were analysed by the least-square fitting program Carbonxs. After heat treatment from 1000 to 2800 °C the interplanar distance of (002) planes decreased from 3.488 to 3.420 Å and the lattice parameter in basal plane increased from 2.440 to 2.464 Å, respectively. Simultaneously, the coherent block size in the basal plane directions increased from 18 to 54 Å, which was accompanied by an increase of the fraction of organised carbon atoms from 0.50 to 0.85. The 002 diffraction profile of the composite was much narrower than the sum of peaks of the matrix and fabric alone. This can probably be caused by a better crystallographic ordering (or by a partial graphitisation) of the matrix in the composite. On the other hand, the composite Young’s modulus slightly decreased with the treatment temperature increasing from 2200 to 2800 °C in spite of the established strong improvement of fibre crystallinity and, therefore, fibre modulus. The mechanisms diminishing the modulus of composite (e.g. partial matrix graphitisation at the fibre/matrix interface and decreasing fibre/matrix contact area) probably prevailed over the increasing contribution of the fibre modulus.