Search results for: non-methane hydrocarbons

Authors: Saheli Mitra, Ramesh Karri, Praveen K. Mylapalli, Arka. B. Dey, Gourav Bhattacharya, Gouriprasanna Roy, Syed M. Kamil, Surajit Dhara, Sunil K. Sinha, Sajal K. Ghosh

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The most well-known structures of lyotropic liquid crystalline systems are the two dimensional hexagonal phase of cylindrical micelles with a positive interfacial curvature and the lamellar phase of flat bilayers with zero interfacial curvature. In aqueous solution of surfactants, the concentration dependent phase transitions have been investigated extensively. However, instead of changing the surfactant concentrations, the local curvature of an aggregate can be altered by tuning the electrostatic interactions among the constituent molecules. Intermediate phases with non-uniform interfacial curvature are still unexplored steps to understand the route of phase transition from hexagonal to lamellar. Understanding such structural evolution in lyotropic liquid crystalline systems is important as it decides the complex rheological behavior of the system, which is one of the main interests of the soft matter industry. Sodium dodecyl sulfate (SDS) is an anionic surfactant and can be considered as a unique system to tune the electrostatics by cationic additives. In present study, imidazolium-based ionic liquids (ILs) with different number of carbon atoms in their single hydrocarbon chain were used as the additive in the aqueous solution of SDS. At a fixed concentration of total non-aqueous components (SDS and IL), the molar ratio of these components was changed, which effectively altered the electrostatic interactions between the SDS molecules. As a result, the local curvature is observed to modify, and correspondingly, the structure of the hexagonal liquid crystalline phases are transformed into other phases. Polarizing optical microscopy of SDS and imidazole-based-IL systems have exhibited different textures of the liquid crystalline phases as a function of increasing concentration of the ILs. The small angle synchrotron x-ray diffraction (SAXD) study has indicated the hexagonal phase of direct cylindrical micelles to transform to a rectangular phase at the presence of short (two hydrocarbons) chain IL. However, the hexagonal phase is transformed to a lamellar phase at the presence of long (ten hydrocarbons) chain IL. Interestingly, at the presence of a medium (four hydrocarbons) chain IL, the hexagonal phase is transformed to another hexagonal phase of direct cylindrical micelles through the lamellar phase. To the best of our knowledge, such a phase sequence has not been reported earlier. Even though the small angle x-ray diffraction study has revealed the lattice parameters of these phases to be similar to each other, their rheological behavior has been distinctly different. These rheological studies have shed lights on how these phases differ in their viscoelastic behavior. Finally, the packing parameters, calculated for these phases based on the geometry of the aggregates, have explained the formation of the self-assembled aggregates.

Keywords: lyotropic liquid crystals, polarizing optical microscopy, rheology, surfactants, small angle x-ray diffraction

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Authors: J. X. Dong, C. J. An, Z. Chen, E. H. Owens, M. C. Boufadel, E. Taylor, K. Lee

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Shorelines are vulnerable to significant environmental impacts from oil spills. Stranded oil can cause potential short- to long-term detrimental effects along beaches that include injuries to the ecosystem, socio-economic and cultural resources. In this study, a three-dimensional (3D) numerical modeling approach is developed to evaluate the fate and transport of spilled oil for hypothetical oiled shoreline cases under various combinations of beach geomorphology and environmental conditions. The developed model estimates the spatial and temporal distribution of spilled oil for the various test conditions, using the finite volume method and considering the physical transport (dispersion and advection), sinks, and sorption processes. The model includes a user-friendly interface for data input on variables such as beach properties, environmental conditions, and physical-chemical properties of spilled oil. An experimental mesoscale tank design was used to test the developed model for dissolved petroleum hydrocarbon within shorelines. The simulated results for effects of different sediment substrates, oil types, and shoreline features for the transport of spilled oil are comparable to those obtained with a commercially available model. Results show that the properties of substrates and the oil removal by shoreline effects have significant impacts on oil transport in the beach area. Sensitivity analysis, through the application of the one-step-at-a-time method (OAT), for the 3D model identified hydraulic conductivity as the most sensitive parameter. The 3D numerical model allows users to examine the behavior of oil on and within beaches, assess potential environmental impacts, and provide technical support for decisions related to shoreline clean-up operations.

Keywords: dissolved petroleum hydrocarbons, environmental multimedia model, finite volume method, sensitivity analysis, total petroleum hydrocarbons

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Authors: Mahshid Davoodpoor, Zahra Shamohammadi Ghahsareh, Saeid Razfar, Alaleh Dabbaghi

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Nowadays, air pollution has become a topic of great concern all over the world. One of the main sources of air pollution is automobile exhaust gas, which introduces a large number of toxic gases, including CO, unburned hydrocarbons (HCs), NOx, and non-methane hydrocarbons (NMHCs), into the air. The application of three-way catalysts (TWCs) is still the most effective strategy to mitigate the emission of these pollutants. Due to the stringent environmental regulations which continuously become stricter, studies on the TWCs are ongoing despite several years of research and development. This arises from the washcoat complexity and the several numbers of parameters involved in the redox reactions. The main objectives of these studies are the optimization of washcoat formulation and the investigation of different coating modes. Perovskite (ABO₃), as a promising class of materials, has unique features that make it versatile to use as an alternative to commonly mixed oxides in washcoats. High catalytic activity for oxidation reactions and its relatively high oxygen storage capacity are important properties of perovskites in catalytic applications. Herein, La₀.₈Ba₀.₂FeO₃ perovskite material was synthesized using the co-precipitation method and characterized by XRD, ICP, and BET analysis. The effect of synthesis conditions, including B site metal (Fe and Co), metal precursor concentration, and dopant (Ba), were examined on the phase purity of the products. The selected perovskite sample was used as one of the components in the TWC formulation to evaluate its catalytic performance through Light-off, oxygen storage capacity, and emission analysis. Results showed a remarkable increment in oxygen storage capacity and also revealed that T50 and emission of CO, HC, and NOx reduced in the presence of perovskite structure which approves the enhancement of catalytic performance for the new washcoat formulation. This study shows the brilliant future of advanced oxide structures in the TWCs.

Keywords: Perovskite, three-way catalyst, PGMs, PGMs reduction

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Authors: Claudio Lamilla, Misael Riquelme, Victoria Saez, Fernanda Sepulveda, Monica Pavez, Leticia Barrientos

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Biosurfactants are compounds synthesized by microorganisms that show various chemical structures, including glycolipids, lipopeptides, polysaccharide-protein complex, phospholipids, and fatty acids. These molecules have attracted attention in recent years due to the amphipathic nature of these compounds, which allows their application in various activities related to emulsification, foaming, detergency, wetting, dispersion and solubilization of hydrophobic compounds. Microorganisms that produce biosurfactants are ubiquitous, not only present in water, soil, and sediments but in extreme conditions of pH, salinity or temperature such as those present in Antarctic ecosystems. Due to this, it is of interest to study biosurfactants producing bacterial strains isolated from Antarctic environments, with the potential to be used in various biotechnological processes. The objective of this research was to characterize biosurfactants produced by bacterial strains isolated from Antarctic environments, with potential use in biotechnological processes for the cleaning of sites contaminated with hydrocarbons. The samples were collected from soils and sediments in the South Shetland Islands and the Antarctic Peninsula, during the Antarctic Research Expedition INACH 2016, from both pristine and human occupied areas (influenced). The bacteria isolation was performed from solid R2A, M1 and LB media. The selection of strains producing biosurfactants was done by hemolysis test on blood agar plates (5%) and blue agar (CTAB). From 280 isolates, it was determined that 10 bacterial strains produced biosurfactants after stimulation with different carbon sources. 16S rDNA taxonomic markers, using the universal primers 27F-1492R, were used to identify these bacterias. Biosurfactants production was carried out in 250 ml flasks using Bushnell Hass liquid culture medium enriched with different carbon sources (olive oil, glucose, glycerol, and hexadecane) during seven days under constant stirring at 20°C. Each cell-free supernatant was characterized by physicochemical parameters including drop collapse, emulsification and oil displacement, as well as stability at different temperatures, salinity, and pH. In addition, the surface tension of each supernatant was quantified using a tensiometer. The strains with the highest activity were selected, and the production of biosurfactants was stimulated in six liters of culture medium. Biosurfactants were extracted from the supernatants with chloroform methanol (2:1). These biosurfactants were tested against crude oil and motor oil, to evaluate their displacement activity (detergency). The characterization by physicochemical properties of 10 supernatants showed that 80% of them produced the drop collapse, 60% had stability at different temperatures, and 90% had detergency activity in motor and olive oil. The biosurfactants obtained from two bacterial strains showed a high activity of dispersion of crude oil and motor oil with halos superior to 10 cm. We can conclude that bacteria isolated from Antarctic soils and sediments provide biological material of high quality for the production of biosurfactants, with potential applications in the biotechnological industry, especially in hydrocarbons -contaminated areas such as petroleum.

Keywords: antarctic, bacteria, biosurfactants, hydrocarbons

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Authors: Chun-Yu Chen, Kua-Rong Wu, Yu-Cheng Chen, Perng-Jy Tsai

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Cooking fumes are known containing polycyclic aromatic hydrocarbons (PAHs) and aldehydes, and some of them have been proven carcinogenic or possibly carcinogenic to humans. Considering their chronic health effects, long-term exposure data is required for assessing cooking workers’ lifetime health risks. Previous exposure assessment studies, due to both time and cost constraints, mostly were based on the cross-sectional data. Therefore, establishing a long-term exposure data has become an important issue for conducting health risk assessment for cooking workers. An approach was proposed in this study. Here, the generation rates of both PAHs and aldehydes from a cooking process were determined by placing a sampling train exactly under the under the exhaust fan under the both the total enclosure condition and normal operating condition, respectively. Subtracting the concentration collected by the former (representing the total emitted concentration) from that of the latter (representing the hood collected concentration), the fugitive emitted concentration was determined. The above data was further converted to determine the generation rates based on the flow rates specified for the exhaust fan. The determinations of the above generation rates were conducted in a testing chamber with a selected cooking process (deep-frying chicken nuggets under 3 L peanut oil at 200°C). The sampling train installed under the exhaust fan consisted respectively an IOM inhalable sampler with a glass fiber filter for collecting particle-phase PAHs, followed by a XAD-2 tube for gas-phase PAHs. The above was also used to sample aldehydes, however, installed with a filter pre-coated with DNPH, and followed by a 2,4-DNPH-cartridge for collecting particle-phase and gas-phase aldehydes, respectively. PAHs and aldehydes samples were analyzed by GC/MS-MS (Agilent 7890B), and HPLC-UV (HITACHI L-7100), respectively. The obtained generation rates of both PAHs and aldehydes were applied to the near-field/ far-field exposure model to estimate the exposures of cooks (the estimated near-field concentration), and helpers (the estimated far-field concentration). For validating purposes, both PAHs and aldehydes samplings were conducted simultaneously using the same sampling train at both near-field and far-field sites of the testing chamber. The sampling results, together with the use of the mixed-effect model, were used to calibrate the estimated near-field/ far-field exposures. In the present study, the obtained emission rates were further converted to emission factor of both PAHs and aldehydes according to the amount of food oil consumed. Applying the long-term food oil consumption records, the emission rates for both PAHs and aldehydes were determined, and the long-term exposure databanks for cooks (the estimated near-field concentration), and helpers (the estimated far-field concentration) were then determined. Results show that the proposed approach was adequate to determine the generation rates of both PAHs and aldehydes under various fan exhaust flow rate conditions. The estimated near-field/ far-field exposures, though were significantly different from that obtained from the field, can be calibrated using the mixed effect model. Finally, the established long-term data bank could provide a useful basis for conducting long-term exposure assessments for cooking workers exposed to PAHs and aldehydes.

Keywords: aldehydes, cooking oil fumes, long-term exposure assessment, modeling, polycyclic aromatic hydrocarbons (PAHs)

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Authors: Maria Trimintziou, Michael Sakellariou, Prodromos Psarropoulos

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Nowadays, the exploitation of hydrocarbons reserves in deep seas and oceans, in combination with the need to transport hydrocarbons among countries, has made the design, construction and operation of offshore pipelines very significant. Under this perspective, it is evident that many more offshore pipelines are expected to be constructed in the near future. Since offshore pipelines are usually crossing extended areas, they may face a variety of geohazards that impose substantial permanent ground deformations (PGDs) to the pipeline and potentially threaten its integrity. In case of a geohazard area, there exist three options to proceed. The first option is to avoid the problematic area through rerouting, which is usually regarded as an unfavorable solution due to its high cost. The second is to apply (if possible) mitigation/protection measures in order to eliminate the geohazard itself. Finally, the last appealing option is to allow the pipeline crossing through the geohazard area, provided that the pipeline will have been verified against the expected PGDs. In areas with moderate or high seismicity the design of an offshore pipeline is more demanding due to the earthquake-related geohazards, such as landslides, soil liquefaction phenomena, and active faults. It is worthy to mention that although worldwide there is a great experience in offshore geotechnics and pipeline design, the experience in seismic design of offshore pipelines is rather limited due to the fact that most of the pipelines have been constructed in non-seismic regions (e.g. North Sea, West Australia, Gulf of Mexico, etc.). The current study focuses on the seismic design of offshore pipelines against active faults. After an extensive literature review of the provisions of the seismic norms worldwide and of the available analytical methods, the study simulates numerically (through finite-element modeling and strain-based criteria) the distress of offshore pipelines subjected to PGDs induced by active seismic faults at the seabed. Factors, such as the geometrical properties of the fault, the mechanical properties of the ruptured soil formations, and the pipeline characteristics, are examined. After some interesting conclusions regarding the seismic vulnerability of offshore pipelines, potential cost-effective mitigation measures are proposed taking into account constructability issues.

Keywords: offhore pipelines, seismic design, active faults, permanent ground deformations (PGDs)

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Authors: Stefan Andersson, Balram Panjwani, Bernd Wittgens, Jan Erik Olsen

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Polycyclic Aromatic hydrocarbons are organic compounds consisting of only hydrogen and carbon aromatic rings. PAH are neutral, non-polar molecules that are produced due to incomplete combustion of organic matter. These compounds are carcinogenic and interact with biological nucleophiles to inhibit the normal metabolic functions of the cells. Norways, the most important sources of PAH pollution is considered to be aluminum plants, the metallurgical industry, offshore oil activity, transport, and wood burning. Stricter governmental regulations regarding emissions to the outer and internal environment combined with increased awareness of the potential health effects have motivated Norwegian metal industries to increase their efforts to reduce emissions considerably. One of the objective of the ongoing industry and Norwegian research council supported "SCORE" project is to reduce potential PAH emissions from an off gas stream of a ferroalloy furnace through controlled combustion. In a dedicated combustion chamber. The sizing and configuration of the combustion chamber depends on the combined properties of the bulk gas stream and the properties of the PAH itself. In order to achieve efficient and complete combustion the residence time and minimum temperature need to be optimized. For this design approach reliable kinetic data of the individual PAH-species and/or groups thereof are necessary. However, kinetic data on the combustion of PAH are difficult to obtain and there is only a limited number of studies. The paper presents an evaluation of the kinetic data for some of the PAH obtained from literature. In the present study, the oxidation is modelled for pure PAH and also for PAH mixed with process gas. Using a perfectly stirred reactor modelling approach the oxidation is modelled including advanced reaction kinetics to study influence of residence time and temperature on the conversion of PAH to CO2 and water. A Chemical Reactor Network (CRN) approach is developed to understand the oxidation of PAH inside the combustion chamber. Chemical reactor network modeling has been found to be a valuable tool in the evaluation of oxidation behavior of PAH under various conditions.

Keywords: PAH, PSR, energy recovery, ferro alloy furnace

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Authors: Sayani Chatterjee, Kusum Lata Pangtey, Sarita Singh, Harvir Singh

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Biodegradation leads to a systematic alteration of the chemical and physical properties of crude oil showing sequential depletion of n-alkane, cycloalkanes, aromatic which increases its specific gravity, viscosity and the abundance of heteroatom-containing compounds. The biodegradation leads to a change in the molecular fingerprints and geochemical parameters of degraded oils, thus make source and maturity identification inconclusive or ambiguous. Asphaltene is equivalent to the most labile part of the respective kerogen and generally has high molecular weight. Its complex chemical structure with substantial microporous units makes it suitable to occlude the hydrocarbon expelled from the source. The occluded molecules are well preserved by the macromolecular structure and thus prevented from secondary alterations. They retain primary organic geochemical information over the geological time. The present study involves the extraction of this occluded hydrocarbon from the asphaltene cage through mild oxidative degradation using mild oxidative reagents like Hydrogen Peroxide (H₂O₂) and Acetic Acid (CH₃COOH) on purified asphaltene of the biodegraded oils of Mansa, Lanwa and Santhal fields in Cambay Basin. The study of these extracted occluded hydrocarbons was carried out for establishing oil to oil and oil to source correlation in the Mehsana block of Cambay Basin. The n-alkane and biomarker analysis through GC and GC-MS of these occluded hydrocarbons show similar biomarker imprint as the normal oil in the area and hence correlatable with them. The abundance of C29 steranes, presence of Oleanane, Gammacerane and 4-Methyl sterane depicts that the oils are derived from terrestrial organic matter deposited in the stratified saline water column in the marine environment with moderate maturity (VRc 0.6-0.8). The oil source correlation study suggests that the oils are derived from Jotana-Warosan Low area. The developed geochemical technique to extract the occluded hydrocarbon has effectively resolved the ambiguity that resulted from the inconclusive fingerprint of the biodegraded oil and the method can be also applied in other biodegraded oils as well.

Keywords: asphaltene, biomarkers, correlation, mild oxidation, occluded hydrocarbon

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Authors: K. Tunde Olagunju, C. Scott Allen, Freek Van Der Meer

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Identification of hydrocarbon oil in remote sensing images is often the first step in monitoring oil during spill events. Most remote sensing methods adopt techniques for hydrocarbon identification to achieve detection in order to model an appropriate cleanup program. Identification on optical sensors does not only allow for detection but also for characterization and quantification. Until recently, in optical remote sensing, quantification and characterization are only potentially possible using high-resolution laboratory and airborne imaging spectrometers (hyperspectral data). Unlike multispectral, hyperspectral data are not freely available, as this data category is mainly obtained via airborne survey at present. In this research, two (2) operational high-resolution multispectral satellites (WorldView-3 and Sentinel-2) are theoretically assessed for their suitability for hydrocarbon characterization, using the hydrocarbon spectral slope model (HYSS). This method utilized the two most persistent hydrocarbon diagnostic/absorption features at 1.73 µm and 2.30 µm for hydrocarbon mapping on multispectral data. In this research, spectra measurement of seven (7) different hydrocarbon oils (crude and refined oil) taken on ten (10) different substrates with the use of laboratory ASD Fieldspec were convolved to Sentinel-2 and WorldView-3 resolution, using their full width half maximum (FWHM) parameter. The resulting hydrocarbon slope values obtained from the studied samples enable clear qualitative discrimination of most hydrocarbons, despite the presence of different background substrates, particularly on WorldView-3. Due to close conformity of central wavelengths and narrow bandwidths to key hydrocarbon bands used in HYSS, the statistical significance for qualitative analysis on WorldView-3 sensors for all studied hydrocarbon oil returned with 95% confidence level (P-value ˂ 0.01), except for Diesel. Using multifactor analysis of variance (MANOVA), the discriminating power of HYSS is statistically significant for most hydrocarbon-substrate combinations on Sentinel-2 and WorldView-3 FWHM, revealing the potential of these two operational multispectral sensors as rapid response tools for hydrocarbon mapping. One notable exception is highly transmissive hydrocarbons on Sentinel-2 data due to the non-conformity of spectral bands with key hydrocarbon absorptions and the relatively coarse bandwidth (> 100 nm).

Keywords: hydrocarbon, oil spill, remote sensing, hyperspectral, multispectral, hydrocarbon-substrate combination, Sentinel-2, WorldView-3

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Authors: Nacira Mecheri, N. Boussid

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A new chemical mechanism designed to study the process of forming the first aromatic ring (benzene) and polycyclic aromatic hydrocarbons (PAH) from a flame of acetylene (C2H2) has been developed. The mechanism developed, contains 50 chemical species involved in 268 reversible elementary reactions. The comparison between the results from modelling and experimental measurements allowed us to test the validity of the postulated mechanism in specific experimental conditions. Kinetic analysis of the flame by calculating the maximum rates for each elementary reaction, allowed us to identify key reactions pathways of consumption and formation of main precursors of soot.

Keywords: benzene, PAH, acetylene, modeling, flame, soot

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: Suraj Sam Issaka, Anita Asamoah, Abass Gibrilla, Joseph Richmond Fianko

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Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds that can form in edible oils during repeated frying and accumulate in fried foods. This study assesses the chances of health risks (carcinogenic and non-carcinogenic) due to PAHs levels in popular finger foods (bean cakes, plantain chips, doughnuts) fried in edible oils (mixed vegetable, sunflower, soybean) from the Ghanaian market. Employing probabilistic health risk assessment that considers variability and uncertainty in exposure and risk estimates provides a more realistic representation of potential health risks. Monte Carlo simulations with 10,000 iterations were used to estimate carcinogenic, mutagenic, and non-carcinogenic risks for different age groups (A: 6-10 years, B: 11-20 years, C: 20-70 years), food types (bean cake, plantain chips, doughnut), oil types (soybean, mixed vegetable, sunflower), and re-usage frying oil frequencies (once, twice, thrice). Our results suggest that, for age Group A, doughnuts posed the highest probability of carcinogenic risk (91.55%) exceeding the acceptable threshold, followed by bean cakes (43.87%) and plantain chips (7.72%), as well as the highest probability of unacceptable mutagenic risk (89.2%), followed by bean cakes (40.32%). Among age Group B, doughnuts again had the highest probability of exceeding carcinogenic risk limits (51.16%) and mutagenic risk limits (44.27%). At the same time, plantain chips exhibited the highest maximum carcinogenic risk. For adults age Group C, bean cakes had the highest probability of unacceptable carcinogenic (50.88%) and mutagenic risks (46.44%), though plantain chips showed the highest maximum values for both carcinogenic and mutagenic risks in this age group. Also, on non-carcinogenic risks across different age groups, it was found that age Group A) who consumed doughnuts had a 68.16% probability of a hazard quotient (HQ) greater than 1, suggesting potential cognitive impairment and lower IQ scores due to early PAH exposure. This group also faced risks from consuming plantain chips and bean cake. For age Group B, the consumption of plantain chips was associated with a 36.98% probability of HQ greater than 1, indicating a potential risk of reduced lung function. In age Group C, the consumption of plantain chips was linked to a 35.70% probability of HQ greater than 1, suggesting a potential risk of cardiovascular diseases.

Keywords: PAHs, fried foods, carcinogenic risk, non-carcinogenic risk, Monte Carlo simulations

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Debdut Roy, Vidyasagar Guggilla

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In this research, we highlight our exploratory work on modified zeolite based catalysts for catalytic cracking of hydrocarbons for production of light olefin i.e. ethylene and propylene. The work is focused on understanding the catalyst structure and activity correlation. Catalysts are characterized by surface area and pore size distribution analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), Temperature Programmed Desorption (TPD) of ammonia, pyridine Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermo-gravimetric Analysis (TGA) and correlated with the catalytic activity. It is observed that the yield of lighter olefins increases with increase of Bronsted acid strength.

Keywords: catalytic cracking, zeolite, propylene, structure-activity correlation

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Authors: Muhammad Zaman Shakir, Mingfa Yao, Zohaib Iqbal

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This study proposed four Jet fuel surrogate (S1, S2 S3, and 4) with careful selection of seven large hydrocarbon fuel components, ranging from C₉-C₁₆ of higher molecular weight and higher boiling point, adapting the standard molecular distribution size of the actual jet fuel. The surrogate was composed of seven components, including n-propyl cyclohexane (C₉H₁₈), n- propylbenzene (C₉H₁₂), n-undecane (C₁₁H₂₄), n- dodecane (C₁₂H₂₆), n-tetradecane (C₁₄H₃₀), n-hexadecane (C₁₆H₃₄) and iso-cetane (iC₁₆H₃₄). The skeletal jet fuel surrogate reaction mechanism was developed by two approaches, firstly based on a decoupling methodology by describing the C₄ -C₁₆ skeletal mechanism for the oxidation of heavy hydrocarbons and a detailed H₂ /CO/C₁ mechanism for prediction of oxidation of small hydrocarbons. The combined skeletal jet fuel surrogate mechanism was compressed into 128 species, and 355 reactions and thereby can be used in computational fluid dynamics (CFD) simulation. The extensive validation was performed for individual single-component including ignition delay time, species concentrations profile and laminar flame speed based on various fundamental experiments under wide operating conditions, and for their blended mixture, among all the surrogate, S1 has been extensively validated against the experimental data in a shock tube, rapid compression machine, jet-stirred reactor, counterflow flame, and premixed laminar flame over wide ranges of temperature (700-1700 K), pressure (8-50 atm), and equivalence ratio (0.5-2.0) to capture the properties target fuel Jet-A, while the rest of three surrogate S2, S3 and S4 has been validated for Shock Tube ignition delay time only to capture the ignition characteristic of target fuel S-8 & GTL, IPK and RP-3 respectively. Based on the newly proposed HyChem model, another four surrogate with similar components and composition, was developed and parallel validations data was used as followed for previously developed surrogate but at high-temperature condition only. After testing the mechanism prediction performance of surrogates developed by the decoupling methodology, the comparison was done with the results of surrogates developed by the HyChem model. It was observed that all of four proposed surrogates in this study showed good agreement with the experimental measurements and the study comes to this conclusion that like the decoupling methodology HyChem model also has a great potential for the development of oxidation mechanism for heavy alkanes because of applicability, simplicity, and compactness.

Keywords: computational fluid dynamics, decoupling methodology Hychem, jet fuel, surrogate, skeletal mechanism

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Authors: Kherbache Radhwane

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This study is concerned with the nature of the strategy of agricultural and rural development, through the fiscal policy adopted by the government throughout programs included in the general budget of the state represented in the national program of agricultural and rural development. This study concluded that the general balance play an important role in the design of the strategy of agricultural and rural development despite the numerous problems clear in the result of the precedent plans of agricultural and rural development. Based on that we suggest that more importance should be accorded to the agricultural and rural field and that it should be one among economic alternatives to the collection of petroleum, as the countryside is the future.

Keywords: general balance, political economy, strategy of agricultural and rural development, economic alternatives, collection of petroleum

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Authors: Amir Gharavi, Mohamed Hassan, Amjad Shah

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The main characteristics of unconventional reservoirs include low-to ultra low permeability and low-to-moderate porosity. As a result, hydrocarbon production from these reservoirs requires different extraction technologies than from conventional resources. An unconventional reservoir must be stimulated to produce hydrocarbons at an acceptable flow rate to recover commercial quantities of hydrocarbons. Permeability for unconventional reservoirs is mostly below 0.1 mD, and reservoirs with permeability above 0.1 mD are generally considered to be conventional. The hydrocarbon held in these formations naturally will not move towards producing wells at economic rates without aid from hydraulic fracturing which is the only technique to assess these tight reservoir productions. Horizontal well with multi-stage fracking is the key technique to maximize stimulated reservoir volume and achieve commercial production. The main objective of this research paper is to investigate development options for a tight mature oilfield. This includes multistage hydraulic fracturing and spacing by building of reservoir models in the Reveal simulator to model potential development options based on sidetracking the existing vertical well. To simulate potential options, reservoir models have been built in the Reveal. An existing Petrel geological model was used to build the static parts of these models. A FBHP limit of 40bars was assumed to take into account pump operating limits and to maintain the reservoir pressure above the bubble point. 300m, 600m and 900m lateral length wells were modelled, in conjunction with 4, 6 and 8 stages of fracs. Simulation results indicate that higher initial recoveries and peak oil rates are obtained with longer well lengths and also with more fracs and spacing. For a 25year forecast, the ultimate recovery ranging from 0.4% to 2.56% for 300m and 1000m laterals respectively. The 900m lateral with 8 fracs 100m spacing gave the highest peak rate of 120m3/day, with the 600m and 300m cases giving initial peak rates of 110m3/day. Similarly, recovery factor for the 900m lateral with 8 fracs and 100m spacing was the highest at 2.65% after 25 years. The corresponding values for the 300m and 600m laterals were 2.37% and 2.42%. Therefore, the study suggests that longer laterals with 8 fracs and 100m spacing provided the optimal recovery, and this design is recommended as the basis for further study.

Keywords: unconventional, resource, hydraulic, fracturing

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Authors: Ali Noorian

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Crude oil contains various compounds of hydrocarbons but low concentrations of inorganic compounds or metals. Vanadium and Nickel are the most common metals in crude oil. These metals usually exist in solution in the oil and residual fuel oil in the refining process is condensed. Deleterious effects of metals in petroleum have been known for some time. These metals do not only contaminate the product but also cause intoxication and loss of catalyst and corrosion to equipment. In this study, removal of heavy metals and petroleum residues were investigated. These methods include physical, chemical and biological treatment processes. For example, processes such as solvent extraction and hydro-catalytic and catalytic methods are effective and practical methods, but typically often have high costs and cause environmental pollution. Furthermore, biological methods that do not cause environmental pollution have been discussed in recent years, but these methods have not yet been industrialized.

Keywords: removal, metal, heavy oil, nickel, vanadium

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Authors: E. Salem

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Combustion has been used for a long time as a means of energy extraction. However, in recent years, there has been a further increase in air pollution, through pollutants such as nitrogen oxides, acid etc. In order to solve this problem, there is a need to reduce carbon and nitrogen oxides through learn burning modifying combustors and fuel dilution. A numerical investigation has been done to investigate the effectiveness of several reduced mechanisms in terms of computational time and accuracy, for the combustion of the hydrocarbons/air or diluted with hydrogen in a micro combustor. The simulations were carried out using the ANSYS Fluent 19.1. To validate the results “PREMIX and CHEMKIN” codes were used to calculate 1D premixed flame based on the temperature, composition of burned and unburned gas mixtures. Numerical calculations were carried for several hydrocarbons by changing the equivalence ratios and adding small amounts of hydrogen into the fuel blends then analyzing the flammable limit, the reduction in NOx and CO emissions, then comparing it to experimental data. By solving the conservations equations, several global reduced mechanisms (2-9-12) were obtained. These reduced mechanisms were simulated on a 2D cylindrical tube with dimensions of 40 cm in length and 2.5 cm diameter. The mesh of the model included a proper fine quad mesh, within the first 7 cm of the tube and around the walls. By developing a proper boundary layer, several simulations were performed on hydrocarbon/air blends to visualize the flame characteristics than were compared with experimental data. Once the results were within acceptable range, the geometry of the combustor was modified through changing the length, diameter, adding hydrogen by volume, and changing the equivalence ratios from lean to rich in the fuel blends, the results on flame temperature, shape, velocity and concentrations of radicals and emissions were observed. It was determined that the reduced mechanisms provided results within an acceptable range. The variation of the inlet velocity and geometry of the tube lead to an increase of the temperature and CO2 emissions, highest temperatures were obtained in lean conditions (0.5-0.9) equivalence ratio. Addition of hydrogen blends into combustor fuel blends resulted in; reduction in CO and NOx emissions, expansion of the flammable limit, under the condition of having same laminar flow, and varying equivalence ratio with hydrogen additions. The production of NO is reduced because the combustion happens in a leaner state and helps in solving environmental problems.

Keywords: combustor, equivalence-ratio, hydrogenation, premixed flames

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Authors: Mohamed Mehdi Kadri

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The prediction of hot shale interval in Silurian formation in a well drilled vertically in Ahnet basin Is by logging Data (Resistivity, Gamma Ray, Sonic) with the calculation of total organic carbon (TOC) using ∆ log R Method. The aim of this paper is to present Physico-chemical Properties of Hot Shale using IR spectroscopy and gas chromatography-mass spectrometry analysis; this mixture of measurements, evaluation and characterization show that the hot shale interval located in the lower of Silurian, the molecules adsorbed at the surface of shale sheet are significantly different from petroleum hydrocarbons this result are also supported with gas-liquid chromatography showed that the study extract is a hydroxypropyl.

Keywords: physic-chemical analysis, reservoirs characterization, sweet window evaluation, Silurian shale, Ahnet basin

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Authors: Suboohi Shervani, Jingjing Ling, Jiabin Liu, Tahir Husain

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Offshore oil-spill has become the most emerging problem in the world. In the current paper, a graphene/ZnO/polymer nanocomposite thin film is coated on stainless steel mesh via layer by layer deposition method. The structural characterization of materials is determined by Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD). The total petroleum hydrocarbons (TPHs) and separation efficiency have been measured via gas chromatography – flame ionization detector (GC-FID). TPHs are reduced to 2 ppm and separation efficiency of the nanocomposite coated mesh is reached ≥ 99% for the final sample. The nanocomposite coated mesh acts as a promising candidate for the separation of oil- water mixture.

Keywords: oil spill, graphene, oil-water separation, nanocomposite

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Authors: Sadeg M. Ghnia, Mahmud Alghattawi

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The NC-210 study area is located in Atshan Saddle between both Ghadamis and Murzuq basins, west Libya. The preserved Palaeozoic successions are predominantly clastics reaching thickness of more than 20,000 ft in northern Ghadamis Basin depocenter. The Carboniferous series consist of interbedded sandstone, siltstone, shale, claystone and minor limestone deposited in a fluctuating shallow marine to brackish lacustrine/fluviatile environment which attain maximum thickness of over 5,000ft in the area of Atshan Saddle and recorded 3,500 ft. in outcrops of Murzuq Basin flanks. The Carboniferous strata was uplifted and eroded during Late Paleozoic and early Mesozoic time in northern Ghadamis Basin and Atshan Saddle. The M'rar Formation age is Tournaisian to Late Serpukhovian based on palynological markers and contains about 12 cycles of sandstone and shale deposited in shallow to outer neritic deltaic settings. The hydrocarbons in the M'rar reservoirs possibly sourced from the Lower Silurian and possibly Frasinian radioactive hot shales. The M'rar Formation lateral, vertical and thickness distribution is possibly influenced by the reactivation of Tumarline Strik-Slip fault and its conjugate faults. A pronounced structural paleohighs and paleolows, trending SE & NW through the Gargaf Saddle, is possibly indicative of the present of two sub-basins in the area of Atshan Saddle. A number of identified seismic reflectors from existing 2D seismic covering Atshan Saddle reflect M’rar deltaic 12 sandstone cycles. M’rar7, M’rar9, M’rar10 and M’rar12 are characterized by high amplitude reflectors, while M’rar2 and M’rar6 are characterized by medium amplitude reflectors. These horizons are productive reservoirs in the study area. Available seismic data in the study area contributed significantly to the identification of M’rar potential traps, which are prominently 3- way dip closure against fault zone. Also seismic data indicates the presence of a significant strikeslip component with the development of flower-structure. The M'rar Formation hydrocarbon discoveries are concentrated mainly in the Atshan Saddle located in southern Ghadamis Basin, Libya and Illizi Basin in southeast of Algeria. Significant additional hydrocarbons may be present in areas adjacent to the Gargaf Uplift, along structural highs and fringing the Hoggar Uplift, providing suitable migration pathways.

Keywords: hydrocarbon potential, stratigraphy, Ghadamis basin, seismic, well data integration

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Authors: Abdelatif Gadoum, Djilali Benyoucef, Mouloudj Hadj, Alla Eddine Toubal Maamar, Mohamed Habib Allah Lahoual

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Hydrogen occurs naturally in the form of chemical compounds, most often in water and hydrocarbons. The main objective of this study is 2D modeling of hydrogen production in inductively coupled plasma in methane at low pressure. In the present model, we include the motions and the collisions of both neutral and charged particles by considering 19 species (i.e in total ; neutrals, radicals, ions, and electrons), and more than 120 reactions (electron impact with methane, neutral-neutral, neutral-ions and surface reactions). The results show that the rate conversion of methane reach 90% and the hydrogen production is about 30%.

Keywords: hydrogen production, inductively coupled plasma, fluid model, methane plasma

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Authors: Haragobinda Srichandan, Ashish Pathak, Dong Jin Kim, Seoung-Won Lee

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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.

Keywords: At. ferrooxidans, bioleaching, metal recovery, spent catalyst

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is the generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups, and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contains four obvious stages, and the main decomposition reaction occurred in the range of 200-600°C. The Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2, and 3 were in the range of 6.67-20.37 kJ for SS; 1.51-6.87 kJ for HZSM5; and 2.29-9.17 kJ for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1, and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with AC and HZSM5 were in the total range of C4-C17, with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds, while with the presence of AC and HZSM5 dropped to 13.02% and 7.3%, respectively. Meanwhile, the generation of benzene, toluene, and xylene (BTX) compounds was significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR, and TGA techniques. Overall, this research demonstrated AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: catalytic pyrolysis, sewage sludge, activated char, HZSM5, bio-oil

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Authors: Margarita S. Tikhonova, Alireza Baniasad, Anton G. Kalmykov, Georgy A. Kalmykov, Ralf Littke

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There is a high complexity in the pore structure of organic-rich rocks caused by the combination of inter-particle porosity from inorganic mineral matter and ultrafine intra-particle porosity from both organic matter and clay minerals. Fluids are retained in that pore space, but there are major uncertainties in how and where the fluids are stored and to what extent they are accessible or trapped in 'closed' pores. A large degree of tortuosity may lead to fractionation of organic matter so that the lighter and flexible compounds would diffuse to the reservoir whereas more complicated compounds may be locked in place. Additionally, parts of hydrocarbons could be bound to solid organic matter –kerogen– and mineral matrix during expulsion and migration. Larger compounds can occupy thin channels so that clogging or oil and gas entrapment will occur. Sequential extraction of applying different solvents is a powerful tool to provide more information about the characteristics of trapped organic matter distribution. The Upper Jurassic – Lower Cretaceous Bazhenov shale is one of the most petroliferous source rock extended in West Siberia, Russia. Concerning the variable mineral composition, pore space distribution and thermal maturation, there are high uncertainties in distribution and composition of organic matter in this formation. In order to address this issue geological and geochemical properties of 30 samples including mineral composition (XRD and XRF), structure and texture (thin-section microscopy), organic matter contents, type and thermal maturity (Rock-Eval) as well as molecular composition (GC-FID and GC-MS) of different extracted materials during sequential extraction were considered. Sequential extraction was performed by a Soxhlet apparatus using different solvents, i.e., n-hexane, chloroform and ethanol-benzene (1:1 v:v) first on core plugs and later on pulverized materials. The results indicate that the studied samples are mainly composed of type II kerogen with TOC contents varied from 5 to 25%. The thermal maturity ranged from immature to late oil window. Whereas clay contents decreased with increasing maturity, the amount of silica increased in the studied samples. According to molecular geochemistry, stored hydrocarbons in open and closed pore space reveal different geochemical fingerprints. The results improve our understanding of hydrocarbon expulsion and migration in the organic-rich Bazhenov shale and therefore better estimation of hydrocarbon potential for this formation.

Keywords: Bazhenov formation, bitumen, molecular geochemistry, sequential extraction

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Authors: L. Sefouhi, M. Djebabra

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Industrial operations have been accompanied by a problem: industrial waste which may be toxic, ignitable, corrosive or reactive. If improperly managed, this waste can pose dangerous health and environmental consequences. The industrial waste management becomes a real problem for them. The oil industry is an important sector in Algeria, from exploration to development and marketing of hydrocarbons. For this sector, industrial wastes pose a big problem. The aim of the present study is to present in a systematic way the subject of industrial waste from the point-of-view of definitions in engineering and legislation. This analysis is necessary, as many different approaches and we will attempt to diagnose the current management of industrial waste, namely an inventory of deposits and methods of sorting, packing, storage, and a description of the different disposal routes. Thus, a proposal for a reasoned and responsible management of waste by avoiding a shift towards future expenses related to the disposal of such waste, and prevents pollution they cause to the environment.

Keywords: industrial waste, environment, management, pollution, risks

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Authors: Muhammad Naeem, Abdulrahman A. Al-Rabiah

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Technical mixture of C4 containing 1-butene and n-butane are very close to each other with respect to their boiling points i.e. -6.3°C for 1-butene and -1°C for n-butane. Extractive distillation process is used for the separation of 1-butene from the existing mixture of C4. The solvent is the essential of extractive distillation, and an appropriate solvent shows an important role in the process economy of extractive distillation. Aspen Plus has been applied for the separation of these hydrocarbons as a simulator; moreover NRTL activity coefficient model was used in the simulation. This model indicated that the material balances in this separation process were accurate for several solvent flow rates. Mixture of acetonitrile and water used as a solvent and 99 % pure 1-butene was separated. This simulation proposed the ratio of the feed to solvent as 1 : 7.9 and 15 plates for the solvent recovery column, previously feed to solvent ratio was more than this and the proposed plates were 30, which can economize the separation process.

Keywords: extractive distillation, 1-butene, Aspen Plus, ACN solvent

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Authors: Zs. Csanádi, A. Szabó Nagy, J. Szabó, J. Erdős

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The main objective of this study was to assess the annual concentration and seasonal variation of benzo(a)pyrene (BaP) associated with PM10 in an urban site of Győr and in a rural site of Sarród in the sampling period of 2008–2012. A total of 280 PM10 aerosol samples were collected in each sampling site and analyzed for BaP by gas chromatography method. The BaP concentrations ranged from undetected to 8 ng/m3 with the mean value of 1.01 ng/m3 in the sampling site of Győr, and from undetected to 4.07 ng/m3 with the mean value of 0.52 ng/m3 in the sampling site of Sarród, respectively. Relatively higher concentrations of BaP were detected in samples collected in both sampling sites in the heating seasons compared with non-heating periods. The annual mean BaP concentrations were comparable with the published data of different other Hungarian sites.

Keywords: air quality, benzo(a)pyrene, PAHs, polycyclic aromatic hydrocarbons

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Authors: Ayten Ekin Meşe, Selahattin Şentürk, Melike Duvanoğlu

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Petroleum refineries are a highly complex process industry with continuous production and high operating costs. Physical separation of crude oil starts with the crude oil distillation unit, continues with various conversion and purification units, and passes through many stages until obtaining the final product. To meet the desired product specification, process parameters are strictly followed. To be able to ensure the quality of distillates, routine analyses are performed in quality control laboratories based on appropriate international standards such as American Society for Testing and Materials (ASTM) standard methods and European Standard (EN) methods. The cut point of distillates in the crude distillation unit is very crucial for the efficiency of the upcoming processes. In order to maximize the process efficiency, the determination of the quality of distillates should be as fast as possible, reliable, and cost-effective. In this sense, an alternative study was carried out on the crude oil distillation unit that serves the entire refinery process. In this work, studies were conducted with three different crude oil distillates which are Light Straight Run Naphtha (LSRN), Heavy Straight Run Naphtha (HSRN), and Kerosene. These products are named after separation by the number of carbons it contains. LSRN consists of five to six carbon-containing hydrocarbons, HSRN consist of six to ten, and kerosene consists of sixteen to twenty-two carbon-containing hydrocarbons. Physical properties of three different crude distillation unit products (LSRN, HSRN, and Kerosene) were determined using Near-Infrared Spectroscopy with multivariate calibration. The absorbance spectra of the petroleum samples were obtained in the range from 10000 cm⁻¹ to 4000 cm⁻¹, employing a quartz transmittance flow through cell with a 2 mm light path and a resolution of 2 cm⁻¹. A total of 400 samples were collected for each petroleum sample for almost four years. Several different crude oil grades were processed during sample collection times. Extended Multiplicative Signal Correction (EMSC) and Savitzky-Golay (SG) preprocessing techniques were applied to FT-NIR spectra of samples to eliminate baseline shifts and suppress unwanted variation. Two different multivariate calibration approaches (Partial Least Squares Regression, PLS and Genetic Inverse Least Squares, GILS) and an ensemble model were applied to preprocessed FT-NIR spectra. Predictive performance of each multivariate calibration technique and preprocessing techniques were compared, and the best models were chosen according to the reproducibility of ASTM reference methods. This work demonstrates the developed models can be used for routine analysis instead of conventional analytical methods with over 90% accuracy.

Keywords: crude distillation unit, multivariate calibration, near infrared spectroscopy, data preprocessing, refinery

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