Search results for: alkanes

Authors: Indira K., Valsamma Joseph, I. S. Bright

Abstract:

Introduction :Biofuels could replace fossil fuels and reduce our carbon footprint on the planet by technological advancements needed for sustainable and economic fuel production. Micro algae have proven to be a promising source to meet the current energy demand because of high lipid content and production of high biomass rapidly. Marine diatoms, which are key contributors in the biofuel sector and also play a significant role in primary productivity and ecology with high biodiversity and genetic and chemical diversity, are less well understood than other microalgae for producing hydrocarbons. Method :The marine diatom samples selected for hydrocarbon analysis were a total of eleven, out of which 9 samples were from the culture collection of NCAAH, and the remaining two of them were isolated by serial dilution method to get a pure culture from a mixed culture of microalgae obtained from the various cruise stations (350&357) FORV Sagar Sampada along the west coast of India. These diatoms were mass cultured in F/2 media, and the biomass harvested. The crude extract was obtained from the biomass by homogenising with n-hexane, and the hydrocarbons was further obtained by passing the crude extract through 500mg Bonna Agela SPE column and the quantitative analysis was done by GCHRMS analysis using HP-5 column and Helium gas was used as a carrier gas(1ml/min). The injector port temperature was 2400C, the detector temperature was 2500C, and the oven was initially kept at 600C for 1 minute and increased to 2200C at the rate of 60C per minute, and the analysis of a mixture of long chain hydrocarbons was done .Results:In the qualitative analysis done, the most potent hydrocarbon was found to be Psammodictyon Panduriforme (NCAAH-9) with a hydrocarbon mass of 37.27mg/g of the biomass and 2.1% of the total biomass 0f 1.395g and the other potent producer is Biddulphia(NCAAH 6) with hydrocarbon mass of 25.4mg/g of biomass and percentage of hydrocarbon is 1.03%. In the quantitative analysis by GCHRMS, the long chain hydrocarbons found in most of the marine diatoms were undecane, hexadecane, octadecane 3ethyl 5,2 ethyl butyl, Eicosane7hexyl, hexacosane, heptacosane, heneicosane, octadecane 3 methyl, triacontane. The exact mass of the long chain hydrocarbons in all the marine diatom samples was found to be Nonadecane 12C191H40, Tritriacontane,13-decyl-13-heptyl 12C501H102, Octadecane,3ethyl-5-(2-ethylbutyl 12C261H54, tetratetracontane 12C441H89, Eicosane, 7-hexyl 12C261H54. Conclusion:All the marine diatoms screened produced long chain hydrocarbons which can be used as diesel fuel with good cetane value example, hexadecane, undecane. All the long chain hydrocarbons can further undergo catalytic cracking to produce short chain alkanes which can give good octane values and can be used as gasoline. Optimisation of hydrocarbon production with the most potent marine diatom yielded long chain hydrocarbons of good fuel quality.

Keywords: biofuel, hydrocarbons, marine diatoms, screening

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Authors: J. C. Colmenares, M. Paszkiewicz-Gawron, D. Lomot, S. R. Pradhan, A. Qayyum

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This work is a report of recent selected experiments of photocatalysis intensification using flow microphotoreactors (fabricated by an ultrasound-based technique) for photocatalytic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) (in the frame of the concept of lignin valorization), and the proof of concept of intensifying a flow selective photocatalytic oxidation process by acoustic cavitation. The synthesized photocatalysts were characterized by using different techniques such as UV-Vis diffuse reflectance spectroscopy, X-ray diffraction, nitrogen sorption, thermal gravimetric analysis, and transmission electron microscopy. More specifically, the work will be on: a Design and development of metal-containing TiO₂ coated microflow reactor for photocatalytic partial oxidation of benzyl alcohol: The current work introduces an efficient ultrasound-based metal (Fe, Cu, Co)-containing TiO₂ deposition on the inner walls of a perfluoroalkoxy alkanes (PFA) microtube under mild conditions. The experiments were carried out using commercial TiO₂ and sol-gel synthesized TiO₂. The rough surface formed during sonication is the site for the deposition of these nanoparticles in the inner walls of the microtube. The photocatalytic activities of these semiconductor coated fluoropolymer based microreactors were evaluated for the selective oxidation of BnOH to PhCHO in the liquid flow phase. The analysis of the results showed that various features/parameters are crucial, and by tuning them, it is feasible to improve the conversion of benzyl alcohol and benzaldehyde selectivity. Among all the metal-containing TiO₂ samples, the 0.5 at% Fe/TiO₂ (both, iron and titanium, as cheap, safe, and abundant metals) photocatalyst exhibited the highest BnOH conversion under visible light (515 nm) in a microflow system. This could be explained by the higher crystallite size, high porosity, and flake-like morphology. b. Designing/fabricating photocatalysts by a sonochemical approach and testing them in the appropriate flow sonophotoreactor towards sustainable selective oxidation of key organic model compounds of lignin: Ultrasonication (US)-assitedprecipitaion and US-assitedhydrosolvothermal methods were used for the synthesis of metal-oxide-based and metal-free-carbon-based photocatalysts, respectively. Additionally, we report selected experiments of intensification of a flow photocatalytic selective oxidation through the use of ultrasonic waves. The effort of our research is focused on the utilization of flow sonophotocatalysis for the selective transformation of lignin-based model molecules by nanostructured metal oxides (e.g., TiO₂), and metal-free carbocatalysts. A plethora of parameters that affects the acoustic cavitation phenomena, and as a result the potential of sonication were investigated (e.g. ultrasound frequency and power). Various important photocatalytic parameters such as the wavelength and intensity of the irradiated light, photocatalyst loading, type of solvent, mixture of solvents, and solution pH were also optimized.

Keywords: heterogeneous photo-catalysis, metal-free carbonaceous materials, selective redox flow sonophotocatalysis, titanium dioxide

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Authors: Colin S. Chen, Chien-Jung Tien, Hsin-Jan Huang

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For weathering studies, the change of chemical constituents by biodegradation effect in diesel-contaminated soils are important factors to be considered, especially when there is a prolonged period of weathering processes. The objective was to evaluate biodegradation effects onto hydrocarbon fingerprinting and distribution patterns of diesel fuels, fuel source screening and differentiation, source-specific marker compounds, and diagnostic ratios of diesel fuel constituents by laboratory and field studies. Biodegradation processes of diesel contaminated soils were evaluated by experiments lasting for 15 and 12 months, respectively. The degradation of diesel fuel in top soils was affected by organic carbon content and biomass of microorganisms in soils. Higher depletion of total petroleum hydrocarbon (TPH), n-alkanes, and polynuclear aromatic hydrocarbons (PAHs) and their alkyl homologues was observed in soils containing higher organic carbon content and biomass. Decreased ratio of selected isoprenoids (i.e., pristane (Pr) and phytane (Ph)) including n-C17/pristane and n-C18/phytane was observed. The ratio of pristane/phytane was remained consistent for a longer period of time. At the end of the experimental period, a decrease of pristane/phytane was observed. Biomarker compounds of bicyclic sesquiterpanes (BS) were less susceptible to the effects of biodegradation. The ratios of characteristic factors such as C15 sesquiterpane/ 8β(H)-drimane (BS3/BS5), C15 sesquiterpane/ 8β(H)-drimane (BS4/BS5), 8β(H)-drimane/8β(H)-homodrimane (BS5/BS10), and C15 sesquiterpane/8β(H)-homodrimane (BS3/BS10) could be adopted for source identification of diesel fuels in top soil. However, for biodegradation processes lasted for six months but shorter than nine months, only BS3/BS5 and BS3/BS10 could be distinguished in two diesel fuels. In subsoil experiments (contaminated soil located 50 cm below), the ratios of characteristic factors including BS3/BS5, BS4/BS5, and BS5/BS10 were valid for source identification of two diesel fuels for nine month biodegradation. At the early stage of contamination, biomass of soil decreased significantly. However, 6 and 7 dominant species were found in soils in top soil experiments, respectively. With less oxygen and nutrients in subsoil, less biomass of microorganisms was observed in subsoils. Only 2 and 4 diesel-degrading species of microorganisms were identified in two soils, respectively. Parameters of double ratio such as fluorene/C1-fluorene: C2-phenanthrene/C3-phenanthrene (C0F/C1F:C2P/C3P) in both top and subsoil, C2-naphthalene/C2-phenanthrene: C1-phenanthrene/C3-phenanthrene (C2N/C2P:C1P/C3P), and C1-phenanthrene/C1-fluorene: C3-naphthalene/C3-phenanthrene (C1P/C1F:C3N/C3P) in subsoil could serve as forensic indicators in diesel contaminated sites. BS3/BS10:BS4/BS5 could be used in 6 to 9 months of biodegradation processes. Results of principal component analysis (PCA) indicated that source identification of diesel fuels in top soil could only be perofrmed for weathering process less than 6 months. For subsoil, identification can be conducted for weathering process less than 9 months. Ratio of isoprenoids (pristane and phytane) and PAHs might be affected by biodegradation in spilled sites. The ratios of bicyclic sesquiterpanes could serve as forensic indicators in diesel-contaminated soils. Finally, source identification was attemped for samples collected from different fuel contaminated sites by using the unique pattern of sesquiterpanes. It was anticipated that the information generated from this study would be adopted by decision makers to evaluate the liability of cleanup in diesel contaminated sites.

Keywords: biodegradation, diagnostic ratio, diesel fuel, environmental forensics

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Authors: Juergen Orasche, Vesta Kohlmeier, George C. Dragan, Gert Jakobi, Patricia Forbes, Ralf Zimmermann

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Underground mining poses a difficult environment for both man and machines. At more than 1000 meters underneath the surface of the earth, ores and other mineral resources are still gained by conventional and motorised mining. Adding to the hazards caused by blasting and stone-chipping, the working conditions are best described by the high temperatures of 35-40°C and high humidity, at low air exchange rates. Separate ventilation shafts lead fresh air into a mine and others lead expended air back to the surface. This is essential for humans and machines working deep underground. Nevertheless, mines are widely ramified. Thus the air flow rate at the far end of a tunnel is sensed to be close to zero. In recent years, conventional mining was supplemented by mining with heavy diesel machines. These very flat machines called Load Haul Dump (LHD) vehicles accelerate and ease work in areas favourable for heavy machines. On the other hand, they emit non-filtered diesel exhaust, which constitutes an occupational hazard for the miners. Combined with a low air exchange, high humidity and inorganic dust from the mining it leads to 'black smog' underneath the earth. This work focuses on the air quality in mines employing LHDs. Therefore we performed personal sampling (samplers worn by miners during their work), stationary sampling and aethalometer (Microaeth MA200, Aethlabs) measurements in a platinum mine in around 1000 meters under the earth’s surface. We compared areas of high diesel exhaust emission with areas of conventional mining where no diesel machines were operated. For a better assessment of health risks caused by air pollution we applied a separated gas-/particle-sampling tool (or system), with first denuder section collecting intermediate VOCs. These multi-channel silicone rubber denuders are able to trap IVOCs while allowing particles ranged from 10 nm to 1 µm in diameter to be transmitted with an efficiency of nearly 100%. The second section is represented by a quartz fibre filter collecting particles and adsorbed semi-volatile organic compounds (SVOC). The third part is a graphitized carbon black adsorber – collecting the SVOCs that evaporate from the filter. The compounds collected on these three sections were analyzed in our labs with different thermal desorption techniques coupled with gas chromatography and mass spectrometry (GC-MS). VOCs and IVOCs were measured with a Shimadzu Thermal Desorption Unit (TD20, Shimadzu, Japan) coupled to a GCMS-System QP 2010 Ultra with a quadrupole mass spectrometer (Shimadzu). The GC was equipped with a 30m, BP-20 wax column (0.25mm ID, 0.25µm film) from SGE (Australia). Filters were analyzed with In-situ derivatization thermal desorption gas chromatography time-of-flight-mass spectrometry (IDTD-GC-TOF-MS). The IDTD unit is a modified GL sciences Optic 3 system (GL Sciences, Netherlands). The results showed black carbon concentrations measured with the portable aethalometers up to several mg per m³. The organic chemistry was dominated by very high concentrations of alkanes. Typical diesel engine exhaust markers like alkylated polycyclic aromatic hydrocarbons were detected as well as typical lubrication oil markers like hopanes.

Keywords: diesel emission, personal sampling, aethalometer, mining

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