Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Catalytic oxidation of sulphide ions to elementary sulphur in aqueous solutions over transition metal oxides

The catalytic activity of a wide range of transition metal oxides in oxidation of sulphide ions by air in aqueous medium was studied. Some specific features of the reaction mechanism on some of the studied oxides were considered. The transition metal oxides are promising catalysts for practical application. Some of these oxides will allow the preparation of catalysts possessing activity comparable to that of the cobalt phthalocyanine based catalysts, popular in industrial practice.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.     

添加剂对尖晶石型锰酸锂性质表征的影响

以LiOH·H_20和MnO_2为原料,分别掺入H_2BO_3、Al_2O_3、SiO_2和P_2O_5等添加剂,用固相分段法制备尖晶石型锰酸锂。结果表明,SiO_2和P_2O_5可以有效地改善LiMn_2O_4的电化学性能,H_3BO_3对锰酸锂的电化学性能影响不大,而Al_2O_3破坏了LiMn_2O_4的电化学性能。面扫描结果显示,Si或P元素各自都均匀地分散于LiMn_2O_4的物相中。从元素电负性和原子半径的角度分析了B、Si、P和Al元素对尖晶石型LiMn_2O_4结构和性能的影响。     

Liquid viscosities and densities of HFC-134a+glycol mixtures

Liquid viscosity and density of six binary mixtures of HFC-134a with glycols [ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (400), and polypropylene glycol (2000)] have been measured in the temperature range from 273 to 333 K. The viscosity was measured by a rolling-ball viscometer calibrated with standard liquids of viscosities and densities (JS5, JS10, JS20, and JS50). The density was measured with a glass pycnometer. The uncertainties of the measurements were estimated to be less than 3.4 % for viscosity and 0.04 % for density, respectively. An equation is given to represent the obtained viscosity values as a function of weight fraction and temperature.     

Probing the early stages of polymerization of ethylene on a model chromium/silica catalyst by Fourier transform infrared spectroscopy

The nature of the interaction of monomer, and the early stages of growth of oligomers of ethylene on a rather more uniform surface of Cr/SiO₂ catalyst than hitherto studied has been investigated by differenceFTIR spectroscopy using C₂D₄ and C₂H₄ as reactants both with and without subsequent treatment of the catalyst with CO andTHF. The active catalyst was prepared by reaction of vapour phase CrO₂Cl₂ with the vicinal hydroxyls of the silica surface. Three distinct kinds of methylene groups were detected. Arguments are given for assigning the peaks at 2935 and 2860 cm^–1 to CH₂ groups directly bound to the active site and those at 2920 and 2850 to CH₂s in the growing chain well removed from the Cr. The peaks at 2160 and 2165 cm^–1 are attributed to CD₂ groups hydrogen bonded to surface hydroxyls.     

Studies on the interactions of metal oxides and Na2 SO4 at 1100 and 1200 K in oxygen

The interaction of different metal oxides such as Co₃O₄, NiO, Al₂O₃, Cr₂O₃, Fe₂O₃ and SiO₂ with Na₂SO₄ at a temperature of 1100 and 1200 K in flowing oxygen has been studied. The thermogravimetric studies for each system were carried out as a function of Na₂SO₄ in the mixture. The presence of different constituents in the reaction products were identified by X-ray diffraction analysis and the morphologies of the reaction products were characterized using metallography and scanning electron microscopy (SEM). The formation of products was also investigated by thermodynamic computation of free energies of the reactions and the study of relevant equilibrium phase diagrams. The soluble species in the aqueous solutions of the reaction products were determined quantitatively using atomic absorption spectrophotometry. The high temperature interaction products usually contain a 3-phase structure namely, Na₂O·M₂O _x , M₂O _x and metal sulphide and/or metal sulphate. The formation of Na₂O·M₂O _x depends upon the solid state solubility of metal oxide in the molten salt at high temperatures. Under limited solubility conditions Na₂O·M₂O _x is invariably formed, but as soon as this condition is relaxed the oxide. M₂O _x , precipitates and forms a separate phase.     

Crystallization behavior of star-shaped poly(ethylene oxide) with cubic silsesquioxane (CSSQ) core

The crystallization behavior of well-defined star-shaped cubic silsesquioxane-poly(ethylene oxide) (CSSQ-PEO) and linear PEO were studied in terms of differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). It was found in DSC analysis that the glass transition temperature (T_g) and the crystallization temperature (T_c) of CSSQ-PEO are different from those of linear PEO. The presence of CSSQ in PEO reduced the overall crystallization growth rate. This effect can be ascribed to the reduction of the mobility of the PEO crystallites in the presence of CSSQ and the star structure of the polymer. The Ozawa method is qualitatively satisfactory for describing the nonisothermal crystallizations of linear PEO and CSSQ-PEO. The presence of CSSQ leads to the diffusion- and nucleation-controlled mechanisms in the crystallization process of CSSQ-PEO whilst only the nucleation-controlled mechanism was observed in the case of linear PEO. The apparent activation energy required for crystallization was calculated using the Kissinger method. The isothermal crystallization morphology of PEO and CSSQ-PEO were also examined by cross-polarizing optical microscopy (CPOM). The CPOM images indicated the spherulite growth is slower in CSSQ-PEO as compared to linear PEO. It was also investigated that more number of PEO spherulites in CSSQ-PEO were observed, which sizes are markedly smaller than the spherulites developed in linear PEO. Wide-angle X-ray scattering (WAXS) studies showed that the crystallization peaks for linear PEO and CSSQ-PEO appeared at different temperature revealing the crystallization process and crystal growth rate are different from each other. However, no significant distortion of the crystal structure of PEO was evaluated in the presence of CSSQ.     

Anodising potential influence on well-ordered nanostructures formed by anodisation of aluminium in sulphuric acid

High-density structures with relatively well-ordered nanopore arrays have been obtained by the self-ordering growth of nanopores occurring during anodisation of aluminium in sulphuric acid. The resulting array of well-ordered nanopores strongly depends on an applied voltage of anodising, temperature and a procedure of synthesis. Regular arranged hexagonal arrays on aluminium with a relatively uniform pore diameter, interpore distance, and depth of pores exceeding 90 μm, can be formed by the self-ordering two-step anodising at 1 °C. The interpore distance and the pore diameter were evaluated on anodised aluminium layers obtained at different cell potentials ranging from 15 to 25 V. The detailed analyses of their uniformity were performed from SEM images. The analysis of a pore arrangement defects was made from SEM top view images taken on samples anodised at various cell potentials. The defect maps, known as Delaunay triangulations, of the arrangement of about 1000 pores were constructed for different applied anodising potentials. The percentage of pores that are not six-fold coordinated by the neighbouring pores indicates the percentage of defected surface.