Physical properties of oleochemical carbonates

Carbonates are a class of compounds that have recently found increasing interest in commercial applications owing to their physical properties and relatively straightforward synthesis. In this work, physical and fuel properties of five straight-chain C_17–39 and three branched C_17–33 oleochemical carbonates were investigated. These properties included cetane number (CN), low-temperature properties, (kinematic) viscosity, lubricity, and surface tension. The carbonates studied had CN ranging from 47 to 107 depending on carbon chain length and branching. For the same number of carbons, the CN of carbonates were lower than those of FA alkyl esters owing to interruption of the CH₂ chain by the carbonate moiety. Kinematic viscosities at 40°C ranged from 4.9 to 22.6 mm²/s whereas m.p. ranged from +3 to below −50°C depending on the carbonate structure. High-frequency reciprocating rig testing showed the neat carbonates to have acceptable lubricity that improved as chain length increased. Finally, the carbonate's ability to influence cold-flow properties in biodiesel (methyl soyate) and lubricity in low-lubricity ultra-low sulfur diesel were examined. The carbonates studied did not significantly affect cold flow or lubricity properties at concentrations up to 10,000 ppm (1 wt%). The properties of the carbonates resemble those of fatty alkyl esters with similar trends resulting from compound structure.     

Size segregation in gas-solid fluidized beds with continuous size distributions

Discrete-particle simulations of a gas-solid fluidized bed are used to investigate the species segregation (de-mixing) behavior of systems with continuous particle size distributions. Both Gaussian and lognormal distributions are investigated over a range of distribution widths, restitution and friction coefficients, and gas velocities. The results indicate that: (i) the average particle diameter decreases as the height within the bed increases, (ii) the level of segregation increases with an increase in the width of the particle size distribution, and (iii) segregation is attenuated as bubbling becomes more vigorous. Furthermore, the shape of the local size distribution (i.e., Gaussian or lognormal) is found to mimic that of the overall size distribution in most regions of the fluidized bed.     

Dehydrogenation of Light Alkanes Over Rhenium Catalysts on Conventional and Mesoporous MFI Supports

Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time on stream due to deactivation of the catalyst. We show that by use of rhenium impregnated MFI supports with very few or no acidic sites (Si/Al > 500), highly selective ethane dehydrogenation catalysts are obtained with ethene selectivities of 98%. By use of mesoporous MFI supports (Si/Al >500) the lifetime of the catalyst appears to be slightly improved compared to conventional MFI crystals. The beneficial effect of a mesoporous MFI support is convincingly demonstrated in propane dehydrogenation, where both conversion and selectivities on the mesoporous MFI (Si/Al > 500) impregnated with Re are significantly higher than on Re supported on a comparable conventional MFI support.     

Mikrostrukturuntersuchungen an porösen Feststoffen durch Physisorptionsmessungen

Studies of the microstructure of porous solids by physisorption measurements . The principal experimental methods for studying the microstructure of porous solids are based on physisorption measurements. The resulting sorption isotherms can yield data such as surface area and pore radius distribution, which are of great importance for development and characterization of porous catalysts. After a brief presentation of available measuring equipment, the main concern of this survey is the evaluation of sorption isotherms. In particular, methods for determining the micropore contribution to the total pore volume and the pore radius distribution in the micropore range are examined critically with regard to their reliability.     

Dependence of oil stability index of fatty compounds on their structure and concentration and presence of metals

During storage and use, vegetable oil-derived industrial products such as biodiesel and biodegradable lubricants can be subjected to conditions that promote oxidation of their unsaturated components. The materials arising during oxidation and subsequent degradation can seriously impair the quality and performance of such products. Therefore, oxidative stability is a significant issue facing these vegetable oil-derived products, and enhanced understanding of the influence of various components of vegetable oils and storage parameters is necessary. In this work, the oil stability index (OSI) was used for assessing oxidation of monoalkyl esters of FA by varying several parameters. Neat fatty compounds and prepared mixtures thereof were studied for assessing the influence of compound structure and concentration. Small amounts of more highly unsaturated compounds had a disproportionately strong effect on oxidative stability. The recently developed concept of bis-allylic equivalents correlated more closely than the iodine value with the OSI times of mixtures of fatty esters. The OSI times of free acids were shorter than those of the corresponding alkyl esters. The presence of copper, iron, and nickel also reduced oxidative stability, but their effect was less than the presence of more highly unsaturated fatty compounds. Of these metals, copper had the strongest catalytic effect on OSI time. OSI may be an alternative to long-term storage tests for determining the influence of extraneous materials such as metals on oxidative stability.     

Carotenoid Composition and Vitamin A Values of Oils from Four Brazilian Palm Fruits

In oils extracted from fresh and sterilized palm fruits (Elaeis guineensis, Jacq. tenera, dura dumpy and psifera and E. oleifera), cis-phytofluene, 13-cis-α-carotene, α-carotene, 13-cis-β-carotene, β-carotene, 9-cis-β-carotene, σ-carotene, zeaxanthin, --cryptoxanthin, poly-cis-lycopene, mono-lycopene and lycopene, were identified and quantified by normal phase open column chromatography (stepwise-elution), TLC, UV/Vis spectroscopy and specific chemical reactions. The sum of α- and β-carotene in all samples analysed was higher than 80% of the total carotenoid content, while the α/β-carotene ratios were W.9, 1/11.1, 1/22 and V2.6 for oils extracted from fresh fruits of dura dumpy, psifera, tenera and E. oleifera, respectively. Total carotenoid contents (pg/g) and vitamin A values (R. E./100 g) of these samples were 1 120.7 and 12 404 for dura dumpy, 283.2 and 3612 for psifera, 660.5 and 7630 for tenera and 1576.8 and 21691 for E. oleifera. The sterilization of fruits (127°C × 35 min.) resulted in isomerization of pigments and reduction of vitamin A values of approximately 45% and 25%, respectively.