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00557 Kinematic viscosity of biodiesel fuel components and related compounds. Influence of compound structure and comparison to petrodiesel fuel components
02 Liquid fuels (sources, properties, recovery) factured combustor were investigated experimentally. A t a term of startup, it is confirmed that vaporization of ethanol was p r o m o t e d by ultrasonic and instantaneous ignition was achieved. V a p o r i z i n g combustion was sustained with recovering a part of its t h e r m a l radiation heat through the porous b u r n e r because A1203 had transparency for light which had near I R wavelength. C o m p l e t e combustion was achieved within A1203 b u r n e r under the equivalence ratio r a n g e d from 0.63 to 0.80, which showed that the combustion m o d e was similar to a premixing combustion. However, NO~ concentration was comparatively high value, 59 97 ppm (02 0% base) in the stable combustion region because a heat value per surface area of the flame was increased due to a local high temperature zone caused by a shortened flame.
06•00554 Effect of process parameters on bitumen emulsions Gingras, J.-P. et al. Chemical Engineering and Processing, 2005, 44, (9), 979 986. B i t u m e n emulsification experiments have been carried out in a continuous pilot scale rotor-stator facility. The effects of the following process parameters, namely the t e m p e r a t u r e of the aqueous phase and bitumen, the rotor speed, the dispersed phase content, the b i t u m e n grade and the emulsion flow rate were investigated. For each process p a r a m e t e r , the trends obtained for the Sauter d i a m e t e r (d3_9 were compared with those available in the literature on emulsification. A new correlation to predict the droplet size was also proposed. It was shown that the droplet viscosity during emulsification, the rotation speed of the rotor and the dispersed phase content have a significant effect on the droplet size.
06•00555 Effects of branching in hexadecylbenzene sulfonate isomers on interfacial tension behavior in oil/alkali systems Yang, J. et al. Fuel, 2005, 84, (12 13), 1607 1611. This paper is concerned with the study of the effect of the molecular structure of surfactant on the reduction of interfacial tension of e n h a n c e d oil recovery ( E O R ) . The interfacial tension behaviour of n o n a n e and crude oil with three hexadecylbenzene sulfonate isomers (with benzene rings located at different positions along the alkyl chains) were investigated. It was found that the interfacial tensions could be reduced to ultra-low values at low alkali concentrations by using a surfactant molecule with a phenyl group located near the centre of the alkyl chain. Molecular structures of this kind were considered to be the most ideal for surfactant flooding. Moreover, the transient low inteffacial tensions in crude oil/alkali system were caused by the synergistic effects between surfactant and the active species g e n e r a t e d at interface, but surfactant molecules played the d o m i n a n t role at equilibrium.
06•00556 Geochemistry of petroleum systems in the Niuzhuang South Slope of Bohai Bay Basin: Part 4. Evidence for new exploration horizons in a maturely explored petroleum province Li, S. et al. Organic Geochemistry, 2005, 36, (8), 1135 1150. Significant oil reserves have been discovered recently in the E k l m e m b e r of the Paleocene E o c e n e Kongdian F o r m a t i o n and the Ordovician 'buried hill' reservoirs in the b a s e m e n t of the N i u z h u a n g South Slope (NSS), Dongying Depression, Bohai Bay Basin. The physical properties and chemical compositions of these oils are different from those in the overlying E o c e n e Oligocene Shahejie F o r m a t i o n (Es), displaying high wax (29 32%,), low sulfur (0.04 0.25%), and high sterane isomerization ratios [0.46 0.52 for C29-gtgtgt sterane 20S/(20S + 20R)]. In contrast, the Es reservoired oils have relatively low wax but high sulfur contents, with the 20S/(20S + 20R) ratio for C~_9-ctctct steranes in the range of 0.33 0.39. Oil-source correlation results show that the Es reservoired oils were derived from source rocks in the Es4 member of the Shahejie F o r m a t i o n within the conventional oil window, whereas the d o m i n a n c e of C29 steranes observed in oils from the E k l and Ordovician reservoirs suggests a c o n t r i b u t i o n from different source(s) for these oils within the deep Es4 interval and the Eke member of the K o n g d i a n F o r m a t i o n . The recent commercial oil discovery in the E k l and older strata and the confirmation of the presence of organic-rich d a r k mudstones in the Eke member of the K o n g d i a n F o r m a t i o n are significant for further petroleum exploration in the deep strata of the D o n g y i n g Depression and other parts of the Bohai Bay Basin.
06•00557 Kinematic viscosity of biodiesel fuel components and related compounds. Influence of compound structure and comparison to petrodiesel fuel components Knothe, G. and Steidley, K. R. Fuel, 2005, 84, (9), 1059 1065. Biodiesel, defined as the mono-alkyl esters of vegetable oils and a n i m a l fats is an alternative diesel fuel that is steadily gaining attention and significance. One of the most i m p o r t a n t fuel properties of biodiesel and conventional diesel fuel derived from p e t r o l e u m is viscosity, which is
also an i m p o r t a n t property of lubricants. R a n g e s of acceptable k i n e m a t i c viscosity are specified in various biodiesel and petrodiesel standards. In this work, the k i n e m a t i c viscosity of n u m e r o u s fatty c o m p o u n d s as well as c o m p o n e n t s of petrodiesel were d e t e r m i n e d at 40:C (ASTM D445) as this is the t e m p e r a t u r e prescribed in biodiesel and petrodiesel standards. The objective is to obtain a database on k i n e m a t i c viscosity under identical conditions that can be used to define the influence of c o m p o u n d structure on k i n e m a t i c viscosity. Kinematic viscosity increases with chain length of either the fatty acid or alcohol moiety in a fatty ester or in an aliphatic hydrocarbon. The increase in k i n e m a t i c viscosity over a certain n u m b e r of carbons is smaller in aliphatic hydrocarbons than in fatty compounds. The k i n e m a t i c viscosity of unsaturated fatty c o m p o u n d s strongly depends on the nature and n u m b e r of double bonds with double bond position affecting viscosity less. T e r m i n a l double bonds in aliphatic hydrocarbons have a comparatively small viscosity-reducing effect. Branching in the alcohol moiety does not significantly affect viscosity c o m p a r e d to straight-chain analogues. Free fatty acids or c o m p o u n d s with hydroxy groups possess significantly higher viscosity. The viscosity range of fatty c o m p o u n d s is greater than that of various hydrocarbons comprising petrodiesel. The effect of dibenzothiophene, a sulfur-containing c o m p o u n d found in petrodiesel fuel, on viscosity of toluene is less than that of fatty esters or long-chain aliphatic hydrocarbons. To further assess the influence of the nature of oxygenated moieties on k i n e m a t i c viscosity, c o m p o u n d s with 10 carbons and varying oxygenated moieties were investigated. A reversal in the effect on viscosity of the carboxylic acid moiety vs. the alcohol moiety is noted for the C10 c o m p o u n d s c o m p a r e d to unsaturated C18 compounds. Overall, the sequence of influence on k i n e m a t i c viscosity of oxygenated moieties is COOH~C OH>COOCH3~C=O>C O C > n o oxygen.
06•00558 Origins of alkylphenols in crude oils: Hydroxylation of alkylbenzenes Bastow, T. P. et al. Organic Geochemistry, 2005, 36, (7), 991 1001. Laboratory experiments involving Lewis-acid catalysed hydroxylation of p r e p a r e d alkylbenzene mixtures of similar composition as found in crude oils, yield alkylphenols in distributions very much like those found in the crude oils. Crude oils with different alkylbenzene distributions have associated differences in their alkylphenol distributions. These can be fully explained through a reaction m e c h a n i s m involving electrophilic aromatic substitution. The results strongly suggest that acid catalysed hydroxylation of alkylbenzenes is a likely formation m e c h a n i s m for alkylphenols present in crude oils. The m e c h a n i s m may also account for the formation of other hydroxylated c o m p o u n d s found in crude oils. The hydroxylation reactions are suggested to take place in the source rock during p e t r o l e u m formation.
06•00559 Palaeoenvironment of the Eocene Eckfeld Maar lake (Germany): implications from geochemical analysis of the oil shale sequence Sabel, M. et al. Organic Geochemistry, 2005, 36, (6), 873 891. Drill core samples from the depth in}erval between 19.4 and 32.0 m of the l a m i n a t e d central lake facies of the E o c e n e Eckfeld M a a r were investigated for b i o m a r k e r and stable isotope composition. Bulk organic geochemical p a r a m e t e r s (C/N, HI) and the molecular composition of the soluble organic m a t t e r indicate a d o m i n a n c e of particulate organic matter from land plants and microbially derived lipids in the lower part of the sedimentary succession. A n angiospermd o m i n a t e d vegetation is indicated from the t e r p e n o i d b i o m a r k e r composition. A b u n d a n t 4-methylsteroids in the 25.6 30.8 m section of the oil shale sequence reflect a contribution of algal-derived biomass. Samples with high concentrations of methylsteroids are characterized by low amounts of triterpenoids related to the a r b o r a n e skeleton, and vice versa. This pattern is i n t e r p r e t e d as reflecting differences in a u t o c h t h o n o u s organic m a t t e r production vs. microbial activity. In the lowermost section (32.0 30.6 m), a trend towards heavier 6 1~ 0 and 6 13C values indicates the evolution of p e r m a n e n t l y meromictic conditions in the lake and an increase in methanogenesis. High 1C values of siderites ( > 10%o) t h r o u g h o u t most of the sequence are consistent with p e r m a n e n t l y anoxic conditions at the s e d i m e n t water interface. The lighter 6 0 values of siderites from turbidites, relative to siderites from biogenic laminites, are postulated to have been caused by t e m p o r a r y phases of increased precipitation, followed by landslides and improved circulation within the lake. D e p l e t i o n of the organic matter in 13C (average (s13C = 29.4%0), in comparison with the fossil wood (ranging from 23.1%o to 26.6%0), is explained by the d o m i n a n c e of waxy, lipid-rich land plant material (e.g. leaf waxes, resins, bark) over wood supplied to the lake. Carbon cycling d u r i n g anoxic decomposition of organic m a t t e r is assumed to further affect the 61SC values through the activity of anaerobic (e.g. m e t h a n o g e n i c ) bacteria, resulting in a depletion of the biomass in 13C. The overall trend in the isotopic composition of organic carbon towards heavier values in the d e p t h interval between 26.0 and 3.2 m is a c c o m p a n i e d by decreasing C/N ratios, indicating an increase in aquatic organic matter production. The geochemistry of the oil shale succession points
Fuel and Energy Abstracts
March 2006
87
06•00554 Effect of process parameters on bitumen emulsions Gingras, J.-P. et al. Chemical Engineering and Processing, 2005, 44, (9), 979 986. B i t u m e n emulsification experiments have been carried out in a continuous pilot scale rotor-stator facility. The effects of the following process parameters, namely the t e m p e r a t u r e of the aqueous phase and bitumen, the rotor speed, the dispersed phase content, the b i t u m e n grade and the emulsion flow rate were investigated. For each process p a r a m e t e r , the trends obtained for the Sauter d i a m e t e r (d3_9 were compared with those available in the literature on emulsification. A new correlation to predict the droplet size was also proposed. It was shown that the droplet viscosity during emulsification, the rotation speed of the rotor and the dispersed phase content have a significant effect on the droplet size.
06•00555 Effects of branching in hexadecylbenzene sulfonate isomers on interfacial tension behavior in oil/alkali systems Yang, J. et al. Fuel, 2005, 84, (12 13), 1607 1611. This paper is concerned with the study of the effect of the molecular structure of surfactant on the reduction of interfacial tension of e n h a n c e d oil recovery ( E O R ) . The interfacial tension behaviour of n o n a n e and crude oil with three hexadecylbenzene sulfonate isomers (with benzene rings located at different positions along the alkyl chains) were investigated. It was found that the interfacial tensions could be reduced to ultra-low values at low alkali concentrations by using a surfactant molecule with a phenyl group located near the centre of the alkyl chain. Molecular structures of this kind were considered to be the most ideal for surfactant flooding. Moreover, the transient low inteffacial tensions in crude oil/alkali system were caused by the synergistic effects between surfactant and the active species g e n e r a t e d at interface, but surfactant molecules played the d o m i n a n t role at equilibrium.
06•00556 Geochemistry of petroleum systems in the Niuzhuang South Slope of Bohai Bay Basin: Part 4. Evidence for new exploration horizons in a maturely explored petroleum province Li, S. et al. Organic Geochemistry, 2005, 36, (8), 1135 1150. Significant oil reserves have been discovered recently in the E k l m e m b e r of the Paleocene E o c e n e Kongdian F o r m a t i o n and the Ordovician 'buried hill' reservoirs in the b a s e m e n t of the N i u z h u a n g South Slope (NSS), Dongying Depression, Bohai Bay Basin. The physical properties and chemical compositions of these oils are different from those in the overlying E o c e n e Oligocene Shahejie F o r m a t i o n (Es), displaying high wax (29 32%,), low sulfur (0.04 0.25%), and high sterane isomerization ratios [0.46 0.52 for C29-gtgtgt sterane 20S/(20S + 20R)]. In contrast, the Es reservoired oils have relatively low wax but high sulfur contents, with the 20S/(20S + 20R) ratio for C~_9-ctctct steranes in the range of 0.33 0.39. Oil-source correlation results show that the Es reservoired oils were derived from source rocks in the Es4 member of the Shahejie F o r m a t i o n within the conventional oil window, whereas the d o m i n a n c e of C29 steranes observed in oils from the E k l and Ordovician reservoirs suggests a c o n t r i b u t i o n from different source(s) for these oils within the deep Es4 interval and the Eke member of the K o n g d i a n F o r m a t i o n . The recent commercial oil discovery in the E k l and older strata and the confirmation of the presence of organic-rich d a r k mudstones in the Eke member of the K o n g d i a n F o r m a t i o n are significant for further petroleum exploration in the deep strata of the D o n g y i n g Depression and other parts of the Bohai Bay Basin.
06•00557 Kinematic viscosity of biodiesel fuel components and related compounds. Influence of compound structure and comparison to petrodiesel fuel components Knothe, G. and Steidley, K. R. Fuel, 2005, 84, (9), 1059 1065. Biodiesel, defined as the mono-alkyl esters of vegetable oils and a n i m a l fats is an alternative diesel fuel that is steadily gaining attention and significance. One of the most i m p o r t a n t fuel properties of biodiesel and conventional diesel fuel derived from p e t r o l e u m is viscosity, which is
also an i m p o r t a n t property of lubricants. R a n g e s of acceptable k i n e m a t i c viscosity are specified in various biodiesel and petrodiesel standards. In this work, the k i n e m a t i c viscosity of n u m e r o u s fatty c o m p o u n d s as well as c o m p o n e n t s of petrodiesel were d e t e r m i n e d at 40:C (ASTM D445) as this is the t e m p e r a t u r e prescribed in biodiesel and petrodiesel standards. The objective is to obtain a database on k i n e m a t i c viscosity under identical conditions that can be used to define the influence of c o m p o u n d structure on k i n e m a t i c viscosity. Kinematic viscosity increases with chain length of either the fatty acid or alcohol moiety in a fatty ester or in an aliphatic hydrocarbon. The increase in k i n e m a t i c viscosity over a certain n u m b e r of carbons is smaller in aliphatic hydrocarbons than in fatty compounds. The k i n e m a t i c viscosity of unsaturated fatty c o m p o u n d s strongly depends on the nature and n u m b e r of double bonds with double bond position affecting viscosity less. T e r m i n a l double bonds in aliphatic hydrocarbons have a comparatively small viscosity-reducing effect. Branching in the alcohol moiety does not significantly affect viscosity c o m p a r e d to straight-chain analogues. Free fatty acids or c o m p o u n d s with hydroxy groups possess significantly higher viscosity. The viscosity range of fatty c o m p o u n d s is greater than that of various hydrocarbons comprising petrodiesel. The effect of dibenzothiophene, a sulfur-containing c o m p o u n d found in petrodiesel fuel, on viscosity of toluene is less than that of fatty esters or long-chain aliphatic hydrocarbons. To further assess the influence of the nature of oxygenated moieties on k i n e m a t i c viscosity, c o m p o u n d s with 10 carbons and varying oxygenated moieties were investigated. A reversal in the effect on viscosity of the carboxylic acid moiety vs. the alcohol moiety is noted for the C10 c o m p o u n d s c o m p a r e d to unsaturated C18 compounds. Overall, the sequence of influence on k i n e m a t i c viscosity of oxygenated moieties is COOH~C OH>COOCH3~C=O>C O C > n o oxygen.
06•00558 Origins of alkylphenols in crude oils: Hydroxylation of alkylbenzenes Bastow, T. P. et al. Organic Geochemistry, 2005, 36, (7), 991 1001. Laboratory experiments involving Lewis-acid catalysed hydroxylation of p r e p a r e d alkylbenzene mixtures of similar composition as found in crude oils, yield alkylphenols in distributions very much like those found in the crude oils. Crude oils with different alkylbenzene distributions have associated differences in their alkylphenol distributions. These can be fully explained through a reaction m e c h a n i s m involving electrophilic aromatic substitution. The results strongly suggest that acid catalysed hydroxylation of alkylbenzenes is a likely formation m e c h a n i s m for alkylphenols present in crude oils. The m e c h a n i s m may also account for the formation of other hydroxylated c o m p o u n d s found in crude oils. The hydroxylation reactions are suggested to take place in the source rock during p e t r o l e u m formation.
06•00559 Palaeoenvironment of the Eocene Eckfeld Maar lake (Germany): implications from geochemical analysis of the oil shale sequence Sabel, M. et al. Organic Geochemistry, 2005, 36, (6), 873 891. Drill core samples from the depth in}erval between 19.4 and 32.0 m of the l a m i n a t e d central lake facies of the E o c e n e Eckfeld M a a r were investigated for b i o m a r k e r and stable isotope composition. Bulk organic geochemical p a r a m e t e r s (C/N, HI) and the molecular composition of the soluble organic m a t t e r indicate a d o m i n a n c e of particulate organic matter from land plants and microbially derived lipids in the lower part of the sedimentary succession. A n angiospermd o m i n a t e d vegetation is indicated from the t e r p e n o i d b i o m a r k e r composition. A b u n d a n t 4-methylsteroids in the 25.6 30.8 m section of the oil shale sequence reflect a contribution of algal-derived biomass. Samples with high concentrations of methylsteroids are characterized by low amounts of triterpenoids related to the a r b o r a n e skeleton, and vice versa. This pattern is i n t e r p r e t e d as reflecting differences in a u t o c h t h o n o u s organic m a t t e r production vs. microbial activity. In the lowermost section (32.0 30.6 m), a trend towards heavier 6 1~ 0 and 6 13C values indicates the evolution of p e r m a n e n t l y meromictic conditions in the lake and an increase in methanogenesis. High 1C values of siderites ( > 10%o) t h r o u g h o u t most of the sequence are consistent with p e r m a n e n t l y anoxic conditions at the s e d i m e n t water interface. The lighter 6 0 values of siderites from turbidites, relative to siderites from biogenic laminites, are postulated to have been caused by t e m p o r a r y phases of increased precipitation, followed by landslides and improved circulation within the lake. D e p l e t i o n of the organic matter in 13C (average (s13C = 29.4%0), in comparison with the fossil wood (ranging from 23.1%o to 26.6%0), is explained by the d o m i n a n c e of waxy, lipid-rich land plant material (e.g. leaf waxes, resins, bark) over wood supplied to the lake. Carbon cycling d u r i n g anoxic decomposition of organic m a t t e r is assumed to further affect the 61SC values through the activity of anaerobic (e.g. m e t h a n o g e n i c ) bacteria, resulting in a depletion of the biomass in 13C. The overall trend in the isotopic composition of organic carbon towards heavier values in the d e p t h interval between 26.0 and 3.2 m is a c c o m p a n i e d by decreasing C/N ratios, indicating an increase in aquatic organic matter production. The geochemistry of the oil shale succession points
Fuel and Energy Abstracts
March 2006
87