Biodiesel production by transesterification of sludge in supercritical conditions

In this study wastewater treatment plant (WWTP) sludge was subjected to a reactive pyrolysis treatment to produce a high quality pyro-oil. Sludge was treated in supercritical conditions in the presence of methanol using hexane as cosolvent in a high pressure lab-autoclave. The variables affecting the pyro-oil yield and the product quality, such as mass ratio of alcohol to sludge, presence of cosolvent and temperature, were investigated. It was found that the use of a non-polar cosolvent (hexane) presents advantages in the production of high quality pyro-oil from sludge: increase of the non-polar pyro-oil yield and a considerable reduction of the amount of methanol needed to carry out the transesterification of fatty acids present in the sludge.

Characterization of Carbon Molecular Sieve Membranes Supported on Ceramic Tubes

Carbon molecular sieve membranes have been analyzed in supported and unsupported configurations in this experimental study. The membranes were used to adsorb CO2, N2 and CH4, and their adsorption data were analyzed to establish differences in rate and capacity of adsorption between the two types of samples (supported and unsupported). Experimental results show an important effect of the support, which can be considered as an additional parameter to tailor pore size on these carbon membranes. Immersion calorimetry values were measured by immersing the membranes into liquids of different molecular dimensions (dichloromethane, benzene, n-hexane, 2,2-dimethylbutane). Similarities were found between adsorption and calorimetric analysis. The pore volume of the samples analyzed ranged from 0.016 to 0.263 cm3/g. The effect of the pyrolysis temperature, either 550 or 700 °C, under N2 atmosphere was also analyzed. Quantification of the pore-size distribution of the support was done by liquid-liquid displacement porosimetry. The composite membrane was used for CO2/CH4 separation before and after pore plugging was done. The ideal selectivity factors value (4.47) was over the Knudsen theoretical factor (0.60) for membrane pyrolyzed at 600 °C, which indicates the potential application of these membranes for the separation of low-molecular weight gases.

Ethanol dehydration via azeotropic distillation with gasoline fractions as entrainers: A pilot-scale study of the manufacture of an ethanol–hydrocarbon fuel blend

We establish experimentally and through simulations the economic and technical viability of dehydrating ethanol by means of azeotropic distillation, using a hydrocarbon as entrainer. The purpose of this is to manufacture a ready-to-use ethanol–hydrocarbon fuel blend. In order to demonstrate the feasibility of this proposition, we have tested an azeotropic water–ethanol feed mixture, using a hydrocarbon as entrainer, in a semi pilot-plant scale distillation column. Four different hydrocarbons (hexane, cyclohexane, isooctane, and toluene) that are representative of the hydrocarbons present in ordinary gasoline have been tested. Each of these hydrocarbons was tested separately in experiments under conditions of constant feed rate and variable reboiler heat duty. The experimentally obtained results are compared with results calculated by a simulator. Finally, the proposed and traditional ethanol dehydration processes are compared to ascertain the advantages of the former over the latter.

Ethanol dehydration via azeotropic distillation with gasoline fraction mixtures as entrainers: A pilot-scale study with industrially produced bioethanol and naphta

Various hydrocarbons (n-hexane, cyclohexane, toluene, isooctane) and mixtures of them (binary, ternary or quaternary), as well as two different types of industrially produced naphtha (one obtained by direct distillation and the other from a catalytic cracking process), have been tested as candidate entrainers to dehydrate ethanol. The tests were carried out in an azeotropic distillation column on a semi pilot plant. The results show that it is possible to dehydrate bioethanol using naphtha as entrainer, obtaining as a result a fuel blend with negligible water content and ready for immediate use in motor vehicles.

Concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs) in liver samples of different marine mammals (1984-2009)

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.

Chromatographic fractionation of bitumen from sediments and presence of glycerol ethers in immature sediments (Table 2)

Alkanes having unusual saturated isoprenoidal and methyl-branched structures have been isolated from the bitumen of several sediments. The methanogenic biomarkers 2,6,10,15,19-pentamethyleicosane and squalane were found in sediments which also contained bacteriogenic glycerol ethers. However, in one ether-containing sediment, 2,6,10,13,17,21-hexamethyldocosane was tentatively identified and this compound was found in place of the established alkane biomarkers. Other hydrocarbons found were regular C21 and C23 isoprenoid alkanes, compounds which cannot be derived from phytol; two isoprenoids of the type 3,7,11.-polymethylalkane, previously reported only in petroleums; 8-methylheptadecane, a probable biomarker for cyanobacteria and a number of its homologs and other methyl-branched alkanes. Ubiquitous branched-chain alkylbenzenes and a homology of trimethylalkylbenzenes were also isolated. Most, or all, of the compounds reported here are probably not catagenetic products but may represent direct algal or bacterial bioinputs.

Hydrocarbon gas concentrations in sediments from ODP Leg 164 sites

Residual concentrations and distributions of hydrocarbon gases from methane to n-heptane were measured in sediments at seven sites on Ocean Drilling Program (ODP) Leg 164. Three sites were drilled at the Cape Fear Diapir of the Carolina Rise, and one site was drilled on the Blake Ridge Diapir. Methane concentrations at these sites result from microbial generation which is influenced by the amount of pore-water sulfate and possible methane oxidation. Methane hydrate was found at the Blake Ridge Diapir site. The other hydrocarbon gases at these sites are likely the product of early microbial processes. Three sites were drilled on a transect of holes across the crest of the Blake Ridge. The base of the zone of gas-hydrate occurrence was penetrated at all three sites. Trends in hydrocarbon gas distributions suggest that methane is microbial in origin and that the hydrocarbon gas mixture is affected by diagenesis, outgassing, and, near the surface, by microbial oxidation. Methane hydrate was recovered at two of these three sites, although gas hydrate is likely present at all three sites. The method used here for determining amounts of residual hydrocarbon gases has its limitations and provides poor assessment of gas distributions, particularly in the stratigraphic interval below about ~100 mbsf. One advantage of the method, however, is that it yields sufficient quantities of gas for other studies such as isotopic determinations.

C4-C7 alkenones in deep sea sediments

It is believed that C4 to C7 hydrocarbons in petroleum are formed by the cracking of organic matter at depths generally exceeding 1,000 m at temperatures in excess of 50 °C (Cordel, 1972; Dow, 1974; Tissot et al., 1974)). Also, none of the alkanes in the butane-heptane range are formed biologically as far as is known at present. Consequently, it is thought that they do not occur in shallow, Recent sediments. In 1962, I analysed 22 samples of Recent sediments from 7 different environments and verified that these hydrocarbons were not present at the p.p.m. level (Dunton and Hunt, 1962) although traces of a few hydrocarbons such as butane, isobutane, isopentane and n-heptane have been found (Sokolov, 1957; Veber and Turkeltaub, 1958; Erdman et al., 1958; Emery and Hoggan, 1958). No identification of individual hexanes or heptanes has been reported except when there has been clear evidence of seepage from deeper source sediments (McIver, 1973).

A unique behavior of sub-critical hydrocarbon permeability in activated carbon at low pressures

In our study on sub-critical hydrocarbon permeation in activated carbon, a minimum in the total permeability (B-T) at low pressure has been observed for only long-chain hydrocarbons such as n-hexane and n-heptane. Such an observation suggests that the minimum appearance depends on the properties of permeating vapors as well as the porous medium. In this paper a permeation model is presented to explain the minimum behavior with the allowance of the collision-reflection factor in the Knudsen diffusivity to be a function of surface loading. Surface diffusion was found to be very significant compared to other transport mechanisms such as Knudsen diffusion and gaseous viscous flow at low pressures. Since the gaseous viscous flow contributes negligibly to the B, at low pressures, the minimum appearance in the B, is mainly attributed to the interplay between Knudsen diffusion and surface diffusion. Also, the molecular structure of adsorbates plays an important role in the minimum appearance.

Catalytic properties of heteropolyacids supported on MCM-41 mesoporous silica for hydrocarbon cracting reactions

It is known that MCM-41 structures have very weak acid sites because of the lack of the bridging hydroxyl groups present in zeolites. Strong acidity however is required for the potential use of these materials in some specific applications such as: cracking and hydrotreating of heavy residue molecules, cracking of waste plastic, etc. The acidity enhancement of the MCM-41 materials was assessed using the n-hexane and polyethylene cracking reactions. MCM-41 samples were impregnated using heteropolyacid (HPA) such as tungestophospheric acid. The catalyst samples were characterized also by x-ray diffraction and benzene adsorption.

Diffusion of linear paraffins in nanoporous silica

The diffusion of hexane, heptane, octane, and decane in nanoporous MCM-41 silica at various temperatures is investigated by the zero-length-column method. The diffusion coefficients are derived by a complete-time-range analysis of desorption curves at different purge flow rates and temperatures. The results show that the calculated low-coverage diffusivity values decrease monotonically, and the derived Henry's law constants increase, as the carbon number of paraffins increases. The study reveals that transport is strongly influenced by intracrystalline diffusion and dominated by the sorbate-sorbent interaction. The diffusion activation energy and adsorption isosteric heat at zero loading increase monotonically with the carbon number of linear paraffins, but their ratio is essentially constant for each adsorbate compound.

Adsorption of flexible n-alkane on graphitized thermal carbon black: analysis of adsorption isotherm by means of GCMC simulation

In this paper, we investigate the suitability of the grand canonical Monte Carlo in the description of adsorption equilibria of flexible n-alkane (butane, pentane and hexane) on graphitized thermal carbon black. Potential model of n-alkane of Martin and Siepmann (J. Phys. Chem. 102 (1998) 2569) is employed in the simulation, and we consider the flexibility of molecule in the simulation. By this we study two models, one is the fully flexible molecular model in which n-alkane is subject to bending and torsion, while the other is the rigid molecular model in which all carbon atoms reside on the same plane. It is found that (i) the adsorption isotherm results of these two models are close to each other, suggesting that n-alkane model behaves mostly as rigid molecules with respect to adsorption although the isotherm for longer chain n-hexane is better described by the flexible molecular model (ii) the isotherms agree very well with the experimental data at least up to two layers on the surface.

In vitro antibacterial activity of Australian native herb extracts against food-related bacteria

The antibacterial activities of water, ethanol and hexane extracts of five Australian herbs (Backhousia citriodora, Anetholea anisata, Eucalyptus staigerana, Eu. olida and Prostanthera incisa) against seven food-related bacteria (Enterococcus faecalis, Escherichia coli, Listeria monocytogenes, Pseudomonas aeruginosa, Salmonella Enteritidis, Sal. Typhimurium and Staphylococcus aureus) were determined by the microtitre broth microdilution assay. The water extracts of all the herbs displayed no or low antimicrobial activity against all of the bacteria tested with the exception of S. aureus. Relatively high levels of activity (minimum inhibitory concentrations of 125-15.6 mu g ml(-1)) against this pathogen were present in water extracts from all herbs except P. incisa. The ethanol and hexane extracts of all herbs displayed some activity against a number of the bacteria tested, with no one particular herb displaying an obviously higher level or range of activity. Staphylococcus aureus proved to be the most sensitive of the bacteria tested against the solvent extracts with all extracts displaying activity ranging from 125 to 7.8 mu g ml(-1), while E. coli and L. monocytogenes, on the other hand, proved the least sensitive with only five of 15 herb/extract combinations displaying any activity against these pathogens. The extracts of the Australian native herbs examined in this study have potential for application in foods to increase shelf-life or promote safety. (c) 2005 Elsevier Ltd. All rights reserved.