Study on the Anti-Coking Nature of Ni/SrTiO3 Catalysts by the CH4 Pyrolysis

A solid phase crystallization (spc) method was applied for the preparation of SrTiO₃-supported Ni catalysts and compared to the impregnation (imp) method. spc-Ni_0.2/SrTiO₃ has highly dispersed and stable Ni metal particles resulting in higher activity and higher sustainability against coking than imp-Ni_0.2/SrTiO₃ in the partial oxidation of CH₄. Both catalysts were tested for the CH₄ pyrolysis in order to elucidate the catalytic nature against coking of spc-Ni_0.2/SrTiO₃. The amount of carbon and the rate of H₂ formation were similar over both catalysts at both 773 and 1073 K. On both catalysts, CH₄ continuously decomposed at 773 K, while the rate of CH₄ pyrolysis quickly decreased at 1073 K. Fibrous carbons grew up with a Ni metal particle on the tip of the fiber at 773 K, while carbon balls and short carbon fibers with a Ni metal particle encapsulated inside formed and no sufficient growth of the fiber was observed at 1073 K. The carbon species formed at 773 K was hydrogenated completely to CH₄ around 873 K, while the hydrogenation of that formed at 1073 K needed higher temperature around 1073 K. However, the carbon species formed on both the catalysts at either 773 or 1073 K was completely oxidized around 773 K. Thus, judging from the anti-coking nature, the behaviors in the CH₄ pyrolysis are similar over both catalysts, nonetheless spc-Ni_0.2/SrTiO₃ was far superior to imp-Ni_0.2/SrTiO₃ in the CH₄ oxidation. It is likely that the high sustainability against coking of spc-Ni_0.2/SrTiO₃ is not due to its intrinsic nature suppressing the coking but due to its high activity of reforming which can quickly eliminate the carbon formed on the catalyst surface.     

n-Hexyl Laurate and Fourteen Related Fatty Acid Esters: New Secretory Compounds from the Julid Millipede, Anaulaciulus sp.

A total of fifteen saturated fatty acid esters were newly identified from the secretions of an unidentified Anaulaciulus sp. (Julida: Julidae). The fatty acid components of the esters were composed of normal chain acids (from C₁₀ to C₁₄) and of branched chain acids (from iso-C₁₂ to iso-C₁₅ and anteiso-C₁₅). The alcohol moieties were all composed of normal chain alcohols varying from n-butanol to n-octanol. The most abundant component found in the total esters was n-hexyl laurate (64.7%). Novel compounds identified from the millipede secretion extracts include six branched iso- and anteiso-fatty esters, an odd-numbered C₁₁-fatty acid ester, a C₁₃-fatty acid ester, and a C₇-alcohol ester, all of which were previously undescribed natural products. In addition, a characteristic mixture of benzoquinones, such as 2-methyl-1,4-benzoquinone, 2-methoxy-3-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, 2-methoxy-6-methyl-1,4-benzoquinone, and 2,3-dimethoxy-5-methyl-1,4-benzoquinone were identified from the secretions, together with trace amounts of 1,4-benzoquinone.     

Carbon dioxide reforming of ethanol over Ni/Y2O3–ZrO2 catalysts

Supported nickel catalysts of composition Ni/Y₂O₃–ZrO₂ were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y₂O₃–ZrO₂ in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO₂ conversion of 61% on the 5NiYZ catalyst at 800 °C, representing a better response than for the catalyst of the same composition prepared by wet impregnation.     

Fluorous Surface‐Active Distannoxane Catalysts

Fluorous distannoxanes (XR^f₂SnOSnR^f₂X)₂⋅n H₂O (R_f=C₆F₁₃C₂H₄) ( 1 : X=C₈F₁₇SO₃, n=10; 4 : X=Cl, n=0) ( 1 ) catalyze the Mukaiyama aldol reaction and the allylation of aldehydes with tetraallyltin at room temperature in fluorous/organic biphasic solvent systems, in which the reactions proceed more rapidly than in a single organic or fluorous solvent. Due to the unique surface activity of 1 , the catalyst, organic substrate(s), and reagent(s) are distributed in both organic and fluorous phases to facilitate smooth reactions. Upon dilution with toluene after the reaction, the catalyst concentrates to the fluorous phase, while the organic substances migrate to the organic phase to effect facile catalyst recovery and recycling. By virtue of such a unique solvophilicity, a new version of fluorous biphase technology has been developed.     

Preparation and properties of biodegradable network poly(ester-carbonate) elastomers

Biodegradable elastomeric network poly(ester-carbonate)s were prepared from multifunctional aliphatic carboxylic acids such as tricarballylic acid (Y_t) or trimesic acid (Y) and polycarbonate diols (PCD) with molecular weights of 1000 and 2000 g/mol. Prepolymers prepared by a melt polycondensation were cast from dimethylformamide solution and postpolymerized at 270 °C for 40-80 min to form a network. The resultant films were transparent, flexible and insoluble in organic solvents. WAXS exhibited the crystalline peaks due to polycarbonate segments for the network films from PCD₂₀₀₀, while those from PCD₁₀₀₀ were amorphous. The tensile properties were determined for these network films at the temperatures 22, 30, 40 and 50 °C. These films showed elastomeric properties at all temperatures measured. The elongation at break was much higher for the films from PCD₂₀₀₀ (208-434%) than those from PCD₁₀₀₀ (40-120%), and decreased with increasing temperatures. The weight losses of the network films degraded in the buffer solution of Rhizopus delemar lipase at 37 °C increased with time, suggesting that these network films are biodegradable. The degradation rate of the network films from Y_t is faster than that from Y. The GPC curves showed that the lipase hydrolyzed both the ester linkages between Y or Y_t and PCD as well as polycarbonate moiety in the network polymer.     

Open dumping site in Asian developing countries: a potential source of polychlorinated dibenz-p-dioxins and polychlorinated dibenzofurans

Open landfill dumping areas for municipal wastes in Asian developing countries have recently received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning of solid wastes, elevated contamination by various toxic chemicals including dioxins and related compounds in these dumping sites has been anticipated. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) were determined in soils from dumping sites in the Philippines, Cambodia, India, and Vietnam. Residue concentrations of PCDD/Fs and coplanar PCBs in dumping site soils were apparently greater than those in soils collected in agricultural or urban areas far from dumping sites, suggesting that dumping sites are potential sources of PCDD/Fs and related compounds. Observed PCDD/F concentrations in soils from dumping sites in the Philippines and Cambodia were comparable or higher than those reported for dioxin-contaminated locations in the world (e.g., near the municipal waste incinerators and open landfill dumping sites). Homologue profiles of PCDD/Fs in dumping site soils from the Philippines and, to a lesser extent, from Cambodia and India reflected patterns of samples representing typical emissions, while profiles of agricultural or urban soils were similar to those of typical environmental sinks. This result suggests recent formation of PCDD/Fs in dumping site areas and that open dumping sites are a potential source of dioxins in Asian developing countries. Uncontrolled combustions of solid wastes by waste pickers, generation of methane gas, and low-temperature burning can be major factors for the formation of dioxins in dumping sites. Elevated fluxes of PCDD/Fs to soils in dumping sites were encountered in the Philippines, Cambodia, India, and Vietnam-Hanoi, and these levels were higher than those reported for other countries. Considerable loading rates of PCDD/Fs in the dumping sites of these countries were observed, ranging from 20 to 3900 mg/yr (0.12-35 mg TEQ/yr). PCDD/F concentrations in some soil samples from the Philippines, Cambodia, India, and Vietnam-Hanoi exceeded environmental guideline values, suggesting potential health effects on humans and wildlife living near these dumping sites. The estimated intakes of dioxins via soil ingestion and dermal exposure for children were higher than those for adults, suggesting greater risk of dioxin exposure for children in dumping sites. To our knowledge, this is the first comprehensive study on PCDD/Fs contamination in open dumping sites of Asian developing countries. On the basis of the result of this study, we have addressed a new environmental issue that open dumping sites are potential sources of PCDD/Fs and related compounds, and dioxin contamination in dumping sites may become a key environmental problem in developing countries.     

Metastable precipitation in isothermally solidified YAG-alumina composites with off-eutectic composition

YAG-alumina composites with Al₂O₃-rich and YAG-rich compositions were prepared by annealing the hot-pressed composites at the eutectic temperature (1820°C) for 1 h followed by cooling down at 10 or 100°C/min in argon atmosphere. Microstructural observations of the solidified composites identified that metastable phase -Al₂O₃ precipitated in the Al₂O₃-rich specimens cooled down at both the cooling rates. For the solidified YAG-rich specimens, however, equilibrium phase -Al₂O₃ could not be reprecipitated, moreover, metastable YAlO₃ phase was formed at cooling rate of 100°C/min. Formation of the metastable phases in the solidified composites was attributed to the decreased melting temperature caused by the divorced eutectic precipitation and the metastable decomposition of YAG component in YAG-alumina eutectic melt during rapid solidification.     

Surface properties of TiFe and TiFe-Nb 6.8 at.% electrodes in aqueous solution

Even at ambient pressure and temperature TiFe and TiFe-Nb 6.8 at.% compounds display their outstanding abilities for absorbing hydrogen when cathodically polarized in an aqueous solution. Electrochemical reaction is also highly activated on electrodes made of these intermetallic compounds. This paper describes the results of electrochemical measurement and the surface properties of both TiFe and TiFe-Nb 6.8 at.% electrodes in comparison with those obtained using TiNi_n and TiCo_n (n = 1, 2, 3), emphasizing catalytic activity for the reaction of hydrogen evolution. It was concluded that the electrochemically active site of TiFe or TiFe-Nb 6.8 at.% electrode surface could be formed only after a specified area of the electrode had been covered with hydrogen of one or a few atomic layers. At the same time, this site acts as an entrance and exit for hydrogen into and out of the electrode.     

Oxidation of mixed copper-iron sulfide

. A rectangular plate of mixed copper-iron sulfide composed of bornite (Cu₅FeS₄) and troilite (FeS) was oxidized in an O₂-Ar mixed gas stream at 1023 to 1123 K. At the start of the oxidation, iron was preferentially oxidized with the rapid formation of a dense Fe₃O₄ layer of about 10 μm thickness on the sample surface, without the evolution of SO₂ gas. Following this reaction, layers of both Fe₃O₄ and Fe₂O₃ grew on the sulfide surface in accordance with the parabolic rate law. The diffusion of iron through the oxide layers was assumed to control the oxidation rate during this stage. The effect of oxygen partial pressure on the parabolic rate constants was minor and an apparent activation energy of 126 kJ/mol was obtained. During the later stages of the reaction, when the sulfur activity in the inner sulfide core increased, the oxidation proceeded irregularly to the interior of the remaining sulfide with the formation of a porous oxide and the evolution of gaseous SO2. The remaining sulfide core was found to be a mixture of bornite (Cu₅FeS₄) and djurleite (Cu_1.96S). H. TSUKADA, former Graduate Student at Kyoto University