Epoxidation of n-hexene and cyclohexene over titanium-containing catalysts

TS-1, Ti-beta and Ti-MCM-41 molecular sieves have been prepared by direct hydrothermal synthesis method and applied to the epoxidation of n-hexene and cyclohexene with H₂O₂ under mild conditions. Ti-beta with extremely low Al content was synthesized by using a seed method to suppress the formation of diol produced by Brønsted acid sites present in Ti-beta. It was also found that a large amount of by-products (1-ol and 1-one) formed over hydrophilic Ti-MCM-41. We further modified Ti-MCM-41 by silylation with bis(trimethylsilyl) trifluoroacetamide (BSTFA). Among these catalysts, the Ti-beta with low content of Al enhanced the yield of epoxide and suppressed the formation of diol markedly. The silylated Ti-MCM-41 reduced the formation of by-products and promoted the yields of epoxide significantly. Based on experimental results, a reaction mechanism with two parallel and competitive reactions was proposed.     

The effects of roasting temperatures on the formation of headspace volatile compounds in perilla seed oil

Volatile compounds of perilla seed oils roasted at different temperatures (150–190°C) were analyzed by dynamic headspace gas chromatography-mass spectrometry. The headspace volatiles in roasted perilla seed oils (RPSO) were composed of thermally produced flavors and compounds originating from the raw perilla seeds. The roasting temperatures significantly affected the production of thermal reaction flavors. Oils from parilla seeds roasted below 170°C had relatively high concentrations of aldehydes, whereas pyrazines and furans were the predominant volatiles above 170°C. In all of the RPSO, the contents of both perilla aldehyde and perilla ketone remained almost constant and might be used to discriminate perilla seed oils from other roasted vegetable seed oils.     

Binary blends of metallocene polyethylene with conventional polyolefins: Rheological and morphological properties

The rheology and morphology of four sets of binary blends of polyethylene synthesized with metallocene catalysis (metallocene polyethylene: MCPE) with polyolefins prepared using Ziegler‐Natta catalysts have been investigated. The blend systems are MCPE with high density polyethylene (MCPE‐HDPE), polypropylene (MCPE‐PP), poly(propylene‐co‐ethylene) (MCPE‐CoPP), and poly(propylene‐co‐ethylene‐co‐1‐butylene) (MCPE‐TerPP). Cole‐Cole plots [storage melt viscosity (η′) versus loss melt viscosity (η″)], plots of the dynamic storage modulus (G′) versus the dynamic loss modulus (G″), and plots of the log melt viscosity (η*, η′, and η″) versus blend compositions were constructed. The morphology of the blends after microtoming and etching was studied. The phase morphology of MCPE‐HDPE appeared homogeneous, whereas the other three blends were heterogeneous. Rheological and morphological investigations indicated that the MCPE‐HDPE blend was miscible, but the other three blends were immiscible in the melt as well as in the solid state. These observations can be rationalized in terms of the similarity of the chemical structures of the polyolefins.     

Blends of ethylene 1‐octene copolymer synthesized by Ziegler–Natta and metallocene catalysts. II. Rheology and morphological behaviors

The rheological and morphological behaviors of commercially available three binary blends of ethylene 1‐octene copolymer (EOC) regarding the melt index (MI), density and comonomer contents, one component made by the Ziegler–Natta and the other by the metallocene catalysts, were investigated to elucidate miscibility and phase behavior. Miscibility of the EOCs blend in a melt state was related to the value of the MI, density, and comonomer content. If the comonomer contents are similar, then the melt viscosity is weight average value, otherwise it is positively or negatively deviated. The microtomed surface prepared by two different cooling processes—one is fast cooling and the other is slow cooling—indicated that all the blends were not homogenous regardless the density, MI, and comonomer content. The Ziegler–Natta catalyzed EOCs exhibited bigger spherulitic diameter and larger ring space than those of the metallocene EOCs prepared by a cooling process. The blends consisting of similar MI showed banded spherulites with different diameter, whereas the blend consisting of different MI and density takes place of explicit phase separation and phase inversion at 1 : 1 blend composition. The melt rheology appeared to influence the mechanical and film properties in the solid state. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1950–1964, 2000     

A study of desulfurization ability and activation energy for CuO-AgO sorbents

In this study, we investigated desulfurization abilities and activation energy using TGA for CuO-AgO sorbents calcined at 700 °C. CuO was used as a main active material and AgO was used as an additive material and 25 wt% SiO₂ was used as a support material. The desulfurization reaction temperatures were 450 °C, 500 °C, and 550 °C and the regeneration reaction temperature was 700 °C. From the TGA experiments, the best sulfur loading of CAS1 sorbent containing 1 wt% AgO was about 14.95 g sulfur/100 g sorbent at 550 °C. The activation energy was calculated by the Chatterjee-Conrad method based on the TGA experiment. Desulfurization ability and activation energy of sorbent were decreased as the content of AgO increased.     

Effect of temperature, oxidant and catalyst loading on the performance of direct formic acid fuel cell

We investigated the effect of temperature, oxidant and catalyst loading on the performance of direct formic acid fuel cell (DFAFC). When oxidant was changed from air to oxygen, the power density was increased to 17.3 mW/ cm² at 25 ‡C. The power density of DFAFC operated with oxygen showed a maximum value of 40.04 mW/cm² with the temperature rise from room temperature to 70 °C. The highest power density of DFAFC using air was observed for Pt-Ru black catalyst with loading of 8 mgPt/cm² at room temperature. At 70 ‡C; however, the performance of catalyst with the loading of 4 mgPt/cm² was higher than that of 8 mgPt/cm². The DFAFC, operated with oxygen and catalyst of 4 mgPt/cm² loading, showed the best performance at all temperature range. The enhancement of cell performance with an increase of catalyst loading is believed to come from an increase of catalyst active sites. However, operated at higher temperature or with oxygen, the cell with higher catalyst loading showed lower performance than expected. It is speculated that the thick catalyst layer inhibits the proton transport.     

Porous silica aerogel/honeycomb ceramic composites fabricated by an ultrasound stimulation process

The synthesis behavior of nanoporous hydrophobic silica aerogel in honeycomb-type ceramics was observed using TEOS and MTES. Silica aerogel in the honeycomb ceramic structure was synthesized under ultrasound stimulation. The synthesized aerogel/honeycomb ceramic composites were dried under supercritical CO₂ drying conditions. The values for the line shrinkage of the wet gels during supercritical CO₂ drying declined from 19% to 4% with an increase in the H₂O/TEOS molar ratio from 8 to 24. Low shrinkage was a key factor in increasing the interface compatibility with the aerogel/honeycomb ceramic composites. The optimum condition of silica aerogel in the honeycomb-type ceramic structure had a TEOS:MTES: H₂O:glycerol ratio equal to 1:1.2:24:0.05 (mol%).     

Stability of Fe/ZSM‐5 de‐NOx catalyst: effects of iron loading and remaining Brønsted acid sites

The stability of Fe/ZSM‐5 de‐NOx catalyst has been investigated. The samples are prepared by sublimation of iron chloride. Substantial amount of protons are found to remain in the fresh catalyst after washing and calcination. After 10 h exposure to wet exhaust gas at 600^°C, the catalyst is severely deactivated. The presence of steam induces dealumination of the ZSM‐5 matrix, because the protons provide the point of attack by water. In addition, highly reactive distorted tetrahedral iron species and tetrahedral species change to less reactive octahedral iron ions or iron agglomerates upon aging treatment. With the second sublimation of iron chloride, the iron loading is increased and thus the concentration of remaining protons is reduced. Also, the catalyst turns out to preserve more reactive iron ions after aging treatment. In conclusion, the second sublimation is believed to bring about a remarkable improvement in the stability of the Fe/ZSM‐5 catalyst although its de‐NOx activity is slightly decreased. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development and validation of a CATHENA fuel channel model for a post-blowdown analysis of the high temperature thermal–chemical experiment CS28-1

To form a licensing basis for a new methodology for a fuel channel safety analysis code for CANDU-6 nuclear reactor, a CATHENA model for a post-blowdown fuel channel analysis has been developed, and tested for a high temperature thermal–chemical experiment CS28-1 [Lei, Q.M., 1993. Post-test analysis of the 28-element high-temperature thermal–chemical experiment CS28-1. In: 4th International Conference on Simulation Methods in Nuclear Engineering, Montreal, PQ, 1993].