Geochemical Study of Natural Bitumen, Condensate and Gas Seeps from Sousse Area, Central Tunisia

Natural hydrocarbon seepage has helped petroleum exploration as a direct indicator of gas and/or oil subsurface accumulations. Surface macro-seeps are generally an indication of a fault in an active Petroleum Seepage System belonging to a Total Petroleum System. This paper describes a case study in which multiple analytical techniques were used to identify and characterize trace petroleum-related hydrocarbons and other volatile organic compounds in groundwater samples collected from Sousse aquifer (Central Tunisia). The analytical techniques used for analyses of water samples included gas chromatography-mass spectrometry (GCMS), capillary GC with flame-ionization detection, Compound Specific Isotope Analysis, Rock Eval Pyrolysis. The objective of the study was to confirm the presence of gasoline and other petroleum products or other volatile organic pollutants in those samples in order to assess the respective implication of each of the potentially responsible parties to the contamination of the aquifer. In addition, the degree of contamination at different depths in the aquifer was also of interest. The oil and gas seeps have been investigated using biomarker and stable carbon isotope analyses to perform oil-oil and oil-source rock correlations. The seepage gases are characterized by high CH4 content, very low δ13CCH4 values (-71,9 ‰) and high C1/C1–5 ratios (0.95–1.0), light deuterium–hydrogen isotope ratios (- 198 ‰) and light δ13CC2 and δ13CCO2 values (-23,8‰ and-23,8‰ respectively) indicating a thermogenic origin with the contribution of the biogenic gas. An organic geochemistry study was carried out on the more ten oil seep samples. This study includes light hydrocarbon and biomarkers analyses (hopanes, steranes, n-alkanes, acyclic isoprenoids, and aromatic steroids) using GC and GC-MS. The studied samples show at least two distinct families, suggesting two different types of crude oil origins: the first oil seeps appears to be highly mature, showing evidence of chemical and/or biological degradation and was derived from a clay-rich source rock deposited in suboxic conditions. It has been sourced mainly by the lower Fahdene (Albian) source rocks. The second oil seeps was derived from a carbonate-rich source rock deposited in anoxic conditions, well correlated with the Bahloul (Cenomanian-Turonian) source rock.

Removal of Polycyclic Aromatic Hydrocarbons Present in Tyre Pyrolytic Oil Using Low Cost Natural Adsorbents

Polycyclic aromatic hydrocarbons (PAHs) are formed during the pyrolysis of scrap tyres to produce tyre pyrolytic oil (TPO). Due to carcinogenic, mutagenic, and toxic properties PAHs are priority pollutants. Hence it is essential to remove PAHs from TPO before utilising TPO as a petroleum fuel alternative (to run the engine). Agricultural wastes have promising future to be utilized as biosorbent due to their cost effectiveness, abundant availability, high biosorption capacity and renewability. Various low cost adsorbents were prepared from natural sources. Uptake of PAHs present in tyre pyrolytic oil was investigated using various low-cost adsorbents of natural origin including sawdust (shisham), coconut fiber, neem bark, chitin, activated charcoal. Adsorption experiments of different PAHs viz. naphthalene, acenaphthalene, biphenyl and anthracene have been carried out at ambient temperature (25°C) and at pH 7. It was observed that for any given PAH, the adsorption capacity increases with the lignin content. Freundlich constant Kf and 1/n have been evaluated and it was found that the adsorption isotherms of PAHs were in agreement with a Freundlich model, while the uptake capacity of PAHs followed the order: activated charcoal> saw dust (shisham) > coconut fiber > chitin. The partition coefficients in acetone-water, and the adsorption constants at equilibrium, could be linearly correlated with octanol–water partition coefficients. It is observed that natural adsorbents are good alternative for PAHs removal. Sawdust of Dalbergia sissoo, a by-product of sawmills was found to be a promising adsorbent for the removal of PAHs present in TPO. It is observed that adsorbents studied were comparable to those of some conventional adsorbents.

Establishment of Air Quality Zones in Italy

Member States shall establish zones and agglomerations throughout their territory to assess and manage air quality in order to comply with European directives. In Italy decree 155/2010, transposing Directive 2008/50/EC on ambient air quality and cleaner air for Europe, merged into a single act the previous provisions on ambient air quality assessment and management, including those resulting from the implementation of Directive 2004/107/EC relating to arsenic, cadmium, nickel, mercury and polycyclic aromatic hydrocarbons in ambient air. Decree 155/2010 introduced stricter rules for identifying zones on the basis of the characteristics of the territory in spite of considering pollution levels, as it was in the past. The implementation of such new criteria has reduced the great variability of the previous zoning, leading to a significant reduction of the total number of zones and to a complete and uniform ambient air quality assessment and management throughout the Country. The present document is related to the new zones definition in Italy according to Decree 155/2010. In particular the paper contains the description and the analysis of the outcome of zoning and classification.

Effect of Fuel Lean Reburning Process on NOx Reduction and CO Emission

Reburning is a useful technology in reducing nitric oxide through injection of a secondary hydrocarbon fuel. In this paper, an experimental study has been conducted to evaluate the effect of fuel lean reburning on NOx/CO reduction in LNG flame. Experiments were performed in flames stabilized by a co-flow swirl burner, which was mounted at the bottom of the furnace. Tests were conducted using LNG gas as the reburn fuel as well as the main fuel. The effects of reburn fuel fraction and injection manner of the reburn fuel were studied when the fuel lean reburning system was applied. The paper reports data on flue gas emissions and temperature distribution in the furnace for a wide range of experimental conditions. At steady state, temperature distribution and emission formation in the furnace have been measured and compared. This paper makes clear that in order to decrease both NOx and CO concentrations in the exhaust when the pulsated fuel lean reburning system was adapted, it is important that the control of some factors such as frequency and duty ratio. Also it shows the fuel lean reburning is also effective method to reduce NOx as much as reburning.

Electrochemical Performance of Carbon Nanotube Based Supercapacitor

Carbon nanotube is one of the most attractive materials for the potential applications of nanotechnology due to its excellent mechanical, thermal, electrical and optical properties. In this paper we report a supercapacitor made of nickel foil electrodes, coated with multiwall carbon nanotubes (MWCNTs) thin film using electrophoretic deposition (EPD) method. Chemical vapor deposition method was used for the growth of MWCNTs and ethanol was used as a hydrocarbon source. High graphitic multiwall carbon nanotube was found at 750oC analyzing by Raman spectroscopy. We observed the electrochemical performance of supercapacitor by cyclic voltammetry. The electrodes of supercapacitor fabricated from MWCNTs exhibit considerably small equivalent series resistance (ESR), and a high specific power density. Electrophoretic deposition is an easy method in fabricating MWCNT electrodes for high performance supercapacitor.

Performance, Emission and Combustion Characteristics of a Variable Compression Ratio Diesel Engine Fueled with Karanj Biodiesel and Its Blends

The use of biodiesel in conventional diesel engines results in substantial reduction of unburned hydrocarbon, carbon monoxide and particulate matters. The performance, emission and combustion characteristics of a single cylinder four stroke variable compression ratio engine when fueled with Karanja (Pongamia) methyl ester and its 10-50 % blends with diesel (on a volume basis) are investigated and compared with standard diesel. The suitability of karanja methyl ester as a biofuel has been established in this study. The useful brake power obtained is similar to diesel fuel for all loads. Experiment has been conducted at a fixed engine speed of 1500 rpm, variable load and at compression ratios of 17.5:1 and 18.5:1. The impact of compression ratio on fuel consumption, combustion pressures and exhaust gas emissions has been investigated and presented. Optimum compression ratio which gives best performance has been identified. The results indicate longer ignition delay, maximum rate of pressure rise, lower heat release rate and higher mass fraction burnt at higher compression ratio for pongamia oil methyl ester when compared to that of diesel. The brake thermal efficiency for pongamia oil methyl ester blends and diesel has been calculated and the blend B20 is found to give maximum thermal efficiency. The blends when used as fuel results in reduction of carbon monoxide, hydrocarbon and increase in nitrogen oxides emissions. PME as an oxygenated fuel generated more complete combustion, which means increased torque and power. This is also supported with higher thermal efficiencies of the PME blends. NOx is slightly increased due to the higher combustion temperature and the presence of fuel oxygen with the blend at full load. PME as a new Biodiesel and its blends can be used in diesel engines without any engine modification.

Catalytic Activity of Aluminum Impregnated Catalysts for the Degradation of Waste Polystyrene

The aluminum impregnated catalysts of Al-alumina (Al-Al2O3), Al-montmorillonite (Al-Mmn) and Al-activated charcoal (Al-AC) of various percent loadings were prepared by wet impregnation method and characterized by SEM, XRD and N2 adsorption/desorption (BET). The catalytic properties were investigated in the degradation of waste polystyrene (WPS). The results of catalytic degradation of Al metal, 20% Al-Al2O3, 5% Al-Mmn and 20% Al-AC were compared with each other for optimum conditions. Among the catalyst used 20% Al-Al2O3 was found the most effective catalyst. The BET surface area of 20% Al-Al2O3 determined was 70.2 m2/g. The SEM data revealed the catalyst with porous structure throughout the frame work with small nanosized crystallites. The yield of liquid products with 20% Al-Al2O3 (91.53 ± 2.27 wt%) was the same as compared to Al metal (91.20 ± 0.35 wt%) but the selectivity of hydrocarbons and yield of styrene monomer (56.32 wt%) was higher with 20% Al-Al2O3 catalyst.  

Heavy Metals and Polycyclic Aromatic Hydrocarbons in Roadside Soil Samples: A Review

Diverse contaminants released into the environment through progress of urbanization and industrialization adversely affect human health. Among various sources of contaminants, especially, in big cities, automobiles play a significant role in aggravating the pollution. Various pollutants viz., heavy metals (Pb, Mn, Ni, Zn, As, Hg, Cd) and Polyaromatic hydrocarbons (Benzo-a-pyrene, fluoranthene, pyrene, benzo-b-anthracene, benzo-b-fluoranthene, acenaphthylene, fluorine, phenantherene, anthracene, chrysene, benzo-k-fluoranthene, benzo-e-pyrene, indenol-1,2,3-cd-pyrene, dibenzo-a,h-anthracene, benzo-ghi-perylene) are released by vehicles. Further, these pollutants are expected to cause severe mutagenic, genotoxic and carcinogenic effects. Considering this, many authors monitored the levels of pollution in roadside soil, water and plants. The present review focuses upon the analysis and effects of heavy metals and polycyclic aromatic hydrocarbons from the roadside samples.

Designing an Optimal Safe Layout for a Fuel Storage Tanks Farm: Case Study of Jaipur Oil Depot

Storage tank farms are essential industrial facilities to accumulate oil, petrochemicals and gaseous products. Since tank farms contain huge mass of fuel and hazardous materials, they are always targets of serious accidents such as fire, explosion, spill and toxic release which may cause severe impacts on human health, environmental and properties. Although having a safe layout is not able to prevent initiating accidents, however it effectively controls and reduces the adverse impact of such accidents. The aim of this paper is to determine the optimal layout for a storage tank contains different type of hydrocarbon fuels. A quantitative risk assessment is carried out on a selected tank farm in Jaipur, India, with particular attention given to both the consequence modeling and the overall risk assessment using PHAST Software. Various designs of tank layouts are examined taking into consideration several issues of plant operations and maintenance. In all stages of the work, standard guidelines specified by the industry are considered and recommendations are substantiated with simulation results and risk quantification.

Effect of Environmental Parameters on the Water Solubility of the Polycyclic Aromatic Hydrocarbons and Derivatives Using Taguchi Experimental Design Methodology

The MIGR’HYCAR research project was initiated to provide decisional tools for risks connected to oil spill drifts in continental waters. These tools aim to serve in the decision-making process once oil spill pollution occurs and/or as reference tools to study scenarios of potential impacts of pollutions on a given site. This paper focuses on the study of the distribution of polycyclic aromatic hydrocarbons (PAHs) and derivatives from oil spill in water as function of environmental parameters. Eight petroleum oils covering a representative range of commercially available products were tested. 41 polycyclic aromatic hydrocarbons (PAHs) and derivates, among them 16 EPA priority pollutants were studied by dynamic tests at laboratory scale. The chemical profile of the water soluble fraction was different from the parent oil profile due to the various water solubility of oil components. Semi-volatile compounds (naphtalenes) constitute the major part of the water soluble fraction. A large variation in composition of the water soluble fraction was highlighted depending on oil type. Moreover, four environmental parameters (temperature, suspended solid quantity, salinity and oil: water surface ratio) were investigated with the Taguchi experimental design methodology. The results showed that oils are divided into three groups: the solubility of Domestic fuel and Jet A1 presented a high sensitivity to parameters studied, meaning they must be taken into account. For Gasoline (SP95-E10) and Diesel fuel, a medium sensitivity to parameters was observed. In fact, the four others oils have shown low sensitivity to parameters studied. Finally, three parameters were found to be significant towards the water soluble fraction.

Isolation of Biosurfactant Producing Spore-Forming Bacteria from Oman: Potential Applications in Bioremediation

Environmental pollution is a global problem and best possible solution is identifying and utilizing native microorganisms. One possible application of microbial product -biosurfactant is in bioremediation of hydrocarbon contaminated sites. We have screened forty two different petroleum contaminated sites from Oman, for biosurfactant producing spore-forming bacterial isolates. Initial screening showed that out of 42 soil samples, three showed reduction in surface tension (ST) and interfacial tension (IFT) within 24h of incubation at 40°C. Out of those 3 soil samples, one was further selected for isolation of bacteria and 14 different bacteria were isolated in pure form. Of those 14 spore-forming, rod shaped bacteria, two showed highest reduction in ST and IFT in the range of 70mN/m to

Vibratinal Spectroscopic Identification of Beta-Carotene in Usnic Acid and PAHs as a Potential Martian Analogue

Raman spectroscopy is currently a part of the instrumentation suite of the ESA ExoMars mission for the remote detection of life signatures in the Martian surface and subsurface. Terrestrial analogues of Martian sites have been identified and the biogeological modifications incurred as a result of extremophilic activity have been studied. Analytical instrumentation protocols for the unequivocal detection of biomarkers in suitable geological matrices are critical for future unmanned explorations, including the forthcoming ESA ExoMars mission to search for life on Mars scheduled for 2018 and Raman spectroscopy is currently a part of the Pasteur instrumentation suite of this mission. Here, Raman spectroscopy using 785nm excitation was evaluated for determining various concentrations of beta-carotene in admixture with polyaromatic hydrocarbons and usnic acid have been investigated by Raman microspectrometry to determine the lowest levels detectable in simulation of their potential identification remotely in geobiological conditions in Martian scenarios. Information from this study will be important for the development of a miniaturized Raman instrument for targetting Martian sites where the biosignatures of relict or extant life could remain in the geological record.

Experimental Investigation of the Effect of Compression Ratio in a Direct Injection Diesel Engine Running on Different Blends of Rice Bran Oil and Ethanol

The performance, emission and combustion characteristics of a single cylinder four stroke variable compression ratio multi fuel engine when fueled with different blends of rice bran oil methyl ester and ethanol are investigated and compared with the results of standard diesel. Bio diesel produced from Rice bran oil by transesterification process has been used in this study. Experiment has been conducted at a fixed engine speed of 1500 rpm, 50% load and at compression ratios of 16.5:1, 17:1, 17.5:1 and 18:1. The impact of compression ratio on fuel consumption, brake thermal efficiency and exhaust gas emissions has been investigated and presented. Optimum compression ratio which gives best performance has been identified. The results indicate longer ignition delay, maximum rate of pressure rise, lower heat release rate and higher mass fraction burnt at higher compression ratio for waste cooking oil methyl ester when compared to that of diesel. The brake thermal efficiency at 50% load for Rice bran oil methyl ester blends and diesel has been calculated and the blend B40 is found to give maximum thermal efficiency. The blends when used as fuel results in reduction of carbon monoxide, hydrocarbon and increase in nitrogen oxides emissions.

Intermolecular Dynamics between Alcohols and Fatty Acid Ester Solvents

This work focused on the interactions which occur between ester solvents and alcohol solutes. The alcohols selected ranged from the simplest alcohol (methanol) to C10-alcohols, and solubility predictions in the form of infinite dilution activity coefficients were made using the Modified UNIFAC Dortmund group contribution model. The model computation was set up on a Microsoft Excel spreadsheet specifically designed for this purpose. It was found that alcohol/ ester interactions yielded an increase in activity coefficients (i.e. became less soluble) with an increase in the size of the ester solvent molecule. Furthermore, activity coefficients decreased with an increase in the size of the alcohol solute. The activity coefficients also decreased with an increase in the degree of unsaturation of the ester hydrocarbon tail. Tertiary alcohols yielded lower activity coefficients than primary alcohols. Finally, cyclic alcohols yielded higher activity coefficients than straight-chain alcohols until a point is reached where the trend is reversed, referred to as the ‘crossover’ point.

Comparison of Bioleaching of Metals from Spent Petroleum Catalyst Using Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

The present investigation deals with bioleaching of spent petroleum catalyst using At. ferrooxidans and At. thiooxidans. The spent catalyst used in the present study was pretreated with acetone to remove the oily hydrocarbons. FESEM and XPS analysis indicated the presence of metals in sulfide and oxide forms in spent catalyst. Both At. ferrooxidans and At. thiooxidans were found to be highly effective in producing the acid. Bioleaching with At. ferrooxidans and At. thiooxidans led to higher recovery of metals compare to control. During bioleaching similar recoveries of metals were obtained using At. ferrooxidans and At. thiooxidans. This might be due to the presence of metals as soluble oxides and sulphides in the spent catalyst. At the end of bioleaching, about 87-90% Ni, 34% Al, 65-73% Mo and 92-97% V were leached using above bacteria. It is elucidated that bioleaching with At. thiooxidans is comparatively more advantageous due to lower cost of sulphur.  

Hydrogen and Biofuel Production from 2-Propanol Over Ru/Al2O3 Catalyst in Supercritical Water

Hydrogen is an important chemical in many industries and it is expected to become one of the major fuels for energy generation in the future. Unfortunately, hydrogen does not exist in its elemental form in nature and therefore has to be produced from hydrocarbons, hydrogen-containing compounds or water. Above its critical point (374.8oC and 22.1MPa), water has lower density and viscosity, and a higher heat capacity than those of ambient water. Mass transfer in supercritical water (SCW) is enhanced due to its increased diffusivity and transport ability. The reduced dielectric constant makes supercritical water a better solvent for organic compounds and gases. Hence, due to the aforementioned desirable properties, there is a growing interest toward studies regarding the gasification of organic matter containing biomass or model biomass solutions in supercritical water. In this study, hydrogen and biofuel production by the catalytic gasification of 2-Propanol in supercritical conditions of water was investigated. Ru/Al2O3 was the catalyst used in the gasification reactions. All of the experiments were performed under a constant pressure of 25 MPa. The effects of five reaction temperatures (400, 450, 500, 550 and 600oC) and five reaction times (10, 15, 20, 25 and 30 s) on the gasification yield and flammable component content were investigated.

Use Cuticular Hydrocarbons as Chemotaxonomic of The Pamphagidae Pamphagus elephas (Insecta, Orthoptera) of Algeria

The cuticular hydrocarbons of Pamphagus elephas (Orthoptera: Pamphagidae) has been analysed by gas chromatography and by combined gas chromatograph-mass spectrometry. The following hydrocarbon classes have been identified in insect cuticular hydrocarbons are: n-alkanes and methylalkanes comprising Monomethyl-, dimethyl-and trimethylalkanes. Sexual dimorphism is observed in long chain alkanes (C24-C36) present on male and female. The cuticulars hydrocarbons of P.elephas ranged from 24 to 36 carbons and incluted n-alkanes, Dimethylalkanes and Trimethylalkanes. nalkanes represented by (C24-C36,72,7% on male and 79,2% on female), internally branched Monomethylalkanes identified were (C25, C30-C32,C35-C37;11% on male and 9,4% on female), Dimethylalkanes detected are (C31-C32, C36; 2,2% on male and 2,06% on female) and Trimethylalkanes detected are (C32, C36; 3,1% on male and 4, 97 on female). Larvae male and female (stage 7) showed the same quality of n-alkanes observed in adults. However a difference quantity is noted.

Viscosity Reduction and Upgrading of Athabasca Oilsands Bitumen by Natural Zeolite Cracking

Oilsands bitumen is an extremely important source of energy for North America. However, due to the presence of large molecules such as asphaltenes, the density and viscosity of the bitumen recovered from these sands are much higher than those of conventional crude oil. As a result the extracted bitumen has to be diluted with expensive solvents, or thermochemically upgraded in large, capital-intensive conventional upgrading facilities prior to pipeline transport. This study demonstrates that globally abundant natural zeolites such as clinoptilolite from Saint Clouds, New Mexico and Ca-chabazite from Bowie, Arizona can be used as very effective reagents for cracking and visbreaking of oilsands bitumen. Natural zeolite cracked oilsands bitumen products are highly recoverable (up to ~ 83%) using light hydrocarbons such as pentane, which indicates substantial conversion of heavier fractions to lighter components. The resultant liquid products are much less viscous, and have lighter product distribution compared to those produced from pure thermal treatment. These natural minerals impart similar effect on industrially extracted Athabasca bitumen.

Ethanol Production from Sugarcane Bagasse by Means of Enzymes Produced by Solid State Fermentation Method

Nowadays there is a growing interest in biofuel production in most countries because of the increasing concerns about hydrocarbon fuel shortage and global climate changes, also for enhancing agricultural economy and producing local needs for transportation fuel. Ethanol can be produced from biomass by the hydrolysis and sugar fermentation processes. In this study ethanol was produced without using expensive commercial enzymes from sugarcane bagasse. Alkali pretreatment was used to prepare biomass before enzymatic hydrolysis. The comparison between NaOH, KOH and Ca(OH)2 shows NaOH is more effective on bagasse. The required enzymes for biomass hydrolysis were produced from sugarcane solid state fermentation via two fungi: Trichoderma longibrachiatum and Aspergillus niger. The results show that the produced enzyme solution via A. niger has functioned better than T. longibrachiatum. Ethanol was produced by simultaneous saccharification and fermentation (SSF) with crude enzyme solution from T. longibrachiatum and Saccharomyces cerevisiae yeast. To evaluate this procedure, SSF of pretreated bagasse was also done using Celluclast 1.5L by Novozymes. The yield of ethanol production by commercial enzyme and produced enzyme solution via T. longibrachiatum was 81% and 50% respectively.

Investigation of the Synthesis of Alcohols Byproducts in Fischer-Tropsch Synthesis on Modified Fe-Cu Catalyst: Reactivity and Mechanism

The influence of copper promoters and reaction conditions on the formation of alcohols byproducts of a common Fischer-Tropsch synthesis used iron-based catalysts were investigated. A good compromise of 28%Cu/FeKLaSiO2 can lead to the optimization of an improved Fischer-Tropsch catalyst. The product distribution shifts towards hydrocarbons with increasing the reaction temperature, while pressure promotes the formation of alcohols. It was found that the production of either alcohols or hydrocarbons followed A-S-F distributions, and their α parameters were essentially different which indicated a competition in the growing chain between the two species. TPD after acetaldehyde adsorption gave strong evidence of the insertion of a C1 oxygen-containing species into an alkyl chain.