Fate of the chlorine and fluorine in a sub-bituminous coal during pyrolysis and gasification

The fate of the chlorine and fluorine present in a sub-bituminous coal from Indonesia during pyrolysis and gasification has been studied with fixed and entrained bed reactors. The rate profile for HCl evolved in the temperature programmed pyrolysis exhibits the main and shoulder peaks at 480 and 600 °C, respectively. Model experiments and subsequent Cl 2p XPS measurements show that HCl reacts with metal impurities and carbon active sites at 500 °C to be retained as inorganic and organic chlorine forms, from which HCl evolves again at elevated temperatures. It is suggested that the HCl observed in the coal pyrolysis may originate from the above-mentioned chlorine functionalities formed by secondary reactions involving the nascent char. In the CO₂ gasification of the 900 °C char at 1000 °C and 2.5 MPa, any measurable amounts of HCl and HF could not be detected even at a high conversion of 75 wt% (daf), suggesting the accumulation of these halogens in the residual char. When the coal is injected into an O₂-blown, entrained bed gasifier at 1200-1400 °C under 2.6 MPa, the partial oxidation proceeds to a larger extent at a higher O₂/coal ratio, whereas the chlorine and fluorine are enriched in the remaining char, and the extent of the enrichment at the latter stage of gasification is larger with the fluorine. The XPS measurements of the chars reveal the presence of the broad F 1 s peak, which can cover a wide range of binding energies attributable to inorganic and organic fluorine. The halogen enrichment during gasification is discussed in terms of secondary reactions of HCl and HF with char.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Decomposition of chlorofluorocarbons on TiO2ZrO2

The decomposition of chlorofluorocarbons (CFCs) in the presence of water was examined over a variety of solid acid catalysts. The TiO₂ZrO₂ catalyst was found to have the highest activity and longest life among the catalysts examined. The activity of the TiO₂ZrO₂ catalysts depended upon the content of TiO₂. At the contents of TiO₂ from 58 to 90 mole%, the TiO₂ZrO₂ catalysts exhibited high activity, and these catalysts were proven to contain TiZrO₄ crystal. From the study of the XRD peak intensity of the TiZrO₄ crystal, it was highest on the TZ-58 which contained 58 mole% of TiO₂, and decreased with increasing the content of TiO₂. Furthermore, the conversion of CFC113 measured at 673 K was highest at TZ-58, and decreased gradually with increasing TiO₂ content. Therefore, the TiZrO₄ crystal influences the activity of decomposition of CFC113. However, the TiO₂ZrO₂ catalyst was gradually deactivated during the reaction due to the elimination of titanium atoms. A good relationship was found between the activity on TiO₂ZrO₂ catalyst and bond energy of CCl in the compounds of chlorofluorocarbons and hydrochlorocarbons, suggesting that the rate controlling step was the cleavage of CCl bond.     

Calibration Curve for Quantitative Analysis of the Monoclinic-Tetragonal ZrO2 System by X-Ray Diffraction

A nonlinear calibration curve for volume fraction vs integrated intensity ratio was obtained for the monoclinic-tetragonal ZrO² system by using X-ray powder pattern-fitting and pattern-decomposition techniques. The empirical equation agrees well with the theoretical one. By using this equation, the deviation from linearity (6.8% maximum) resulting from the intensity difference of corresponding reflections of the two phases can be estimated quite accurately.     

Isotachophoretic analysis of surfactants

The qualitative and quantitative determination of anionic surfactants (sodium and lithium alkylsulfate, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl sulfosuccinate, sodium and lithium perfluoroalkylcarboxylate, and lithium perfluorooctanesulfonate) were investigated by a capillary tube isotachophoresis using a potential gradient detector. The leading electrolyte solution was the mixture of acetonitrile and aqueous solution of histidine buffer containing calcium chloride. The terminating electrolyte solution was the aqueous solution of sodium octanoate. These electrolytes were effective for the analysis of the mixtures of strongly acidic surfactants.     

High-Resolution Electron Microscopy Observations of Stacking Faults in β-SiC

Structural images of the stacking faults in β-SiC were obtained with a high-resolution electron microscope. Stacking faults initially present in β-SiC powder particles were eliminated as grain growth proceeded at elevated temperatures.     

The electrocatalytic activities of the Pd-doped MnO2 for the chlorine evolution reaction

The anodic evolution of chlorine on the massive β-MnO₂ doped with various amounts of Pd was investigated in acidic chloride solution. A second-order relation was found between the rate of the chlorine evolution reaction and the number of active Pd sites at the electrode surface. And it was confirmed that, in the relatively low doped electrodes, the active sites are more effectively dispersed on the surface with microscopic homogeneity. From the activation energies, it was also suggested that the reaction mechanism on the MnO₂ doped with relatively small amounts of Pd is somewhat different from that on the pure PdO electrode.     

Novel method of preparing Ag–Hg alloy on polyacrylamide films and their structure

A novel method is proposed of preparing thin Ag–Hg alloy on PAAm film surface at room temperature: The film of interest is formed by holding PAAm aqueous solution with AgNO₃ in Hg-saturated atmosphere. Two kinds of films, one of which is a conductor and the other an insulator, can be selectively formed with pH-controlled PAAm solution by ammonia. The conducting surface is assigned to the α phase of Ag–Hg alloy by means of X-ray analysis. Potentiometric titration and IR spectral studies suggest the existence of PAAm–Ag⁺ complexes. On the basis of their structure and the oxidation and reduction potential of Ag⁺ and Hg²⁺, the mechanism of film formation is also discussed.     

Built-in Nanostructures in Transparent Oxides for Novel Photonic and Electronic Functions Materials

We review distinct photonic/electronic properties originating from built-in nanostructures in transparent oxide-based materials, emphasizing potential of nanostructures hidden in crystal structure. Materials focused on are oxychalcogenides LaCuOCh (Ch = chalcogen ion) and homologous oxides InGaO₃(ZnO)_m(m = integer) having naturally formed multi-quantum well structures and 12CaO· 7Al₂O₃ (C12A7) with a unique nanoporous structure. Novel functions and devices arising from the built-in nanostructure are: (1) modulation doping of positive holes and room-temperature stable exciton in LaCuOCh, (2) high-performance transparent field-effect transistor fabricated in InGaO₃(ZnO)₅ epitaxial thin films, and (3) conversion of insulator to persistent electronic conductor by carrier doping in 12CaO·7Al₂O₃ (C12A7).     

Synthesis of nitrogen incorporated diamond-like carbon thin films using microwave surface-wave plasma CVD

Nitrogenated diamond-like (DLC:N) carbon thin films have been deposited by microwave surface wave plasma chemical vapor deposition on silicon and quartz substrates, using argon gas, camphor dissolved in ethyl alcohol composition and nitrogen as plasma source. The deposited DLC:N films were characterized for their chemical, optical, structural and electrical properties through X-ray photoelectron spectroscopy, UV/VIS/NIR spectroscopy, Raman spectroscopy, atomic force microscope and current–voltage characteristics. Optical band gap decreased (2.7 to 2.4 eV) with increasing Ar gas flow rate. The photovoltaic measurements of DLC:N / p-Si structure show that the open-circuit voltage (V_oc) of 168.8 mV and a short-circuit current density (J_sc) of 8.4 μA/cm² under light illumination (AM 1.5 100 mW/cm²). The energy conversion efficiency and fill factor were found to be 3.4 × 10^{− 4}% and 0.238 respectively.