Search results for: chlorinated aliphatic hydrocarbons
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 400

Search results for: chlorinated aliphatic hydrocarbons

70 The Spatial and Temporal Distribution of Ambient Benzene, Toluene, Ethylbenzene and Xylene Concentrations at an International Airport in South Africa

Authors: Ryan S. Johnson, Raeesa Moolla

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Airports are known air pollution hotspots due to the variety of fuel driven activities that take place within the confines of them. As such, people working within airports are particularly vulnerable to exposure of hazardous air pollutants, including hundreds of aromatic hydrocarbons, and more specifically a group of compounds known as BTEX (viz. benzene, toluene, ethyl-benzene and xylenes). These compounds have been identified as being harmful to human and environmental health. Through the use of passive and active sampling methods, the spatial and temporal variability of benzene, toluene, ethyl-benzene and xylene concentrations within the international airport was investigated. Two sampling campaigns were conducted. In order to quantify the temporal variability of concentrations within the airport, an active sampling strategy using the Synspec Spectras Gas Chromatography 955 instrument was used. Furthermore, a passive sampling campaign, using Radiello Passive Samplers was used to quantify the spatial variability of these compounds. In addition, meteorological factors are known to affect the dispersal and dilution of pollution. Thus a Davis Pro-Weather 2 station was utilised in order to measure in situ weather parameters (viz. wind speed, wind direction and temperature). Results indicated that toluene varied on a daily, temporal scale considerably more than other concentrations. Toluene further exhibited a strong correlation with regards to the meteorological parameters, inferring that toluene was affected by these parameters to a greater degree than the other pollutants. The passive sampling campaign revealed BTEXtotal concentrations ranged between 12.95 – 124.04 µg m-3. From the results obtained it is clear that benzene, toluene, ethyl-benzene and xylene concentrations are heterogeneously spatially dispersed within the airport. Due to the slow wind speeds recorded over the passive sampling campaign (1.13 m s-1.), the hotspots were located close to the main concentration sources. The most significant hotspot was located over the main apron of the airport. It is recommended that further, extensive investigations into the seasonality of hazardous air pollutants at the airport is necessary in order for sound conclusions to be made about the temporal and spatial distribution of benzene, toluene, ethyl-benzene and xylene concentrations within the airport.

Keywords: airport, air pollution hotspot, BTEX concentrations, meteorology

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69 Human Health Risk Assessment from Metals Present in a Soil Contaminated by Crude Oil

Authors: M. A. Stoian, D. M. Cocarta, A. Badea

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The main sources of soil pollution due to petroleum contaminants are industrial processes involve crude oil. Soil polluted with crude oil is toxic for plants, animals, and humans. Human exposure to the contaminated soil occurs through different exposure pathways: Soil ingestion, diet, inhalation, and dermal contact. The present study research is focused on soil contamination with heavy metals as a consequence of soil pollution with petroleum products. Human exposure pathways considered are: Accidentally ingestion of contaminated soil and dermal contact. The purpose of the paper is to identify the human health risk (carcinogenic risk) from soil contaminated with heavy metals. The human exposure and risk were evaluated for five contaminants of concern of the eleven which were identified in soil. Two soil samples were collected from a bioremediation platform from Muntenia Region of Romania. The soil deposited on the bioremediation platform was contaminated through extraction and oil processing. For the research work, two average soil samples from two different plots were analyzed: The first one was slightly contaminated with petroleum products (Total Petroleum Hydrocarbons (TPH) in soil was 1420 mg/kgd.w.), while the second one was highly contaminated (TPH in soil was 24306 mg/kgd.w.). In order to evaluate risks posed by heavy metals due soil pollution with petroleum products, five metals known as carcinogenic were investigated: Arsenic (As), Cadmium (Cd), ChromiumVI (CrVI), Nickel (Ni), and Lead (Pb). Results of the chemical analysis performed on samples collected from the contaminated soil evidence soil contamination with heavy metals as following: As in Site 1 = 6.96 mg/kgd.w; As in Site 2 = 11.62 mg/kgd.w, Cd in Site 1 = 0.9 mg/kgd.w; Cd in Site 2 = 1 mg/kgd.w; CrVI was 0.1 mg/kgd.w for both sites; Ni in Site 1 = 37.00 mg/kgd.w; Ni in Site 2 = 42.46 mg/kgd.w; Pb in Site 1 = 34.67 mg/kgd.w; Pb in Site 2 = 120.44 mg/kgd.w. The concentrations for these metals exceed the normal values established in the Romanian regulation, but are smaller than the alert level for a less sensitive use of soil (industrial). Although, the concentrations do not exceed the thresholds, the next step was to assess the human health risk posed by soil contamination with these heavy metals. Results for risk were compared with the acceptable one (10-6, according to World Human Organization). As, expected, the highest risk was identified for the soil with a higher degree of contamination: Individual Risk (IR) was 1.11×10-5 compared with 8.61×10-6

Keywords: carcinogenic risk, heavy metals, human health risk assessment, soil pollution

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68 Organic Geochemical Evaluation of the Ecca Group Shale: Implications for Hydrocarbon Potential

Authors: Temitope L. Baiyegunhi, Kuiwu Liu, Oswald Gwavava, Christopher Baiyegunhi

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Shale gas has recently been the exploration focus for future energy resource in South Africa. Specifically, the black shales of the lower Ecca Group in the study area are considered to be one of the most prospective targets for shale gas exploration. Evaluation of this potential resource has been restricted due to the lack of exploration and scarcity of existing drill core data. Thus, only limited previous geochemical data exist for these formations. In this study, outcrop and core samples of the Ecca Group were analysed to assess their total organic carbon (TOC), organic matter type, thermal maturity and hydrocarbon generation potential (SP). The results show that these rocks have TOC ranging from 0.11 to 7.35 wt.%. The SP values vary from 0.09 to 0.53 mg HC/g, suggesting poor hydrocarbon generative potential. The plot of S1 versus TOC shows that the source rocks were characterized by autochthonous hydrocarbons. S2/S3 values range between 0.40 and 7.5, indicating Type- II/III, III, and IV kerogen. With the exception of one sample from the collingham formation which has HI value of 53 mg HC/g TOC, all other samples have HI values of less than 50 mg HC/g TOC, thus suggesting Type-IV kerogen, which is mostly derived from reworked organic matter (mainly dead carbon) with little or no potential for hydrocarbon generation. Tmax values range from 318 to 601℃, indicating immature to over-maturity of hydrocarbon. The vitrinite reflectance values range from 2.22 to 3.93%, indicating over-maturity of the kerogen. Binary plots of HI against OI and HI versus Tmax show that the shales are of Type II and mixed Type II-III kerogen, which are capable of generating both natural gas and minor oil at suitable burial depth. Based on the geochemical data, it can be inferred that the source rocks are immature to over-matured variable from localities and have potential of producing wet to dry gas at present-stage. Generally, the Whitehill formation of the Ecca Group is comparable to the Marcellus and Barnett Shales. This further supports the assumption that the Whitehill Formation has a high probability of being a profitable shale gas play, but only when explored in dolerite-free area and away from the Cape Fold Belt.

Keywords: source rock, organic matter type, thermal maturity, hydrocarbon generation potential, Ecca Group

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67 Improved Technology Portfolio Management via Sustainability Analysis

Authors: Ali Al-Shehri, Abdulaziz Al-Qasim, Abdulkarim Sofi, Ali Yousef

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The oil and gas industry has played a major role in improving the prosperity of mankind and driving the world economy. According to the International Energy Agency (IEA) and Integrated Environmental Assessment (EIA) estimates, the world will continue to rely heavily on hydrocarbons for decades to come. This growing energy demand mandates taking sustainability measures to prolong the availability of reliable and affordable energy sources, and ensure lowering its environmental impact. Unlike any other industry, the oil and gas upstream operations are energy-intensive and scattered over large zonal areas. These challenging conditions require unique sustainability solutions. In recent years there has been a concerted effort by the oil and gas industry to develop and deploy innovative technologies to: maximize efficiency, reduce carbon footprint, reduce CO2 emissions, and optimize resources and material consumption. In the past, the main driver for research and development (R&D) in the exploration and production sector was primarily driven by maximizing profit through higher hydrocarbon recovery and new discoveries. Environmental-friendly and sustainable technologies are increasingly being deployed to balance sustainability and profitability. Analyzing technology and its sustainability impact is increasingly being used in corporate decision-making for improved portfolio management and allocating valuable resources toward technology R&D.This paper articulates and discusses a novel workflow to identify strategic sustainable technologies for improved portfolio management by addressing existing and future upstream challenges. It uses a systematic approach that relies on sustainability key performance indicators (KPI’s) including energy efficiency quotient, carbon footprint, and CO2 emissions. The paper provides examples of various technologies including CCS, reducing water cuts, automation, using renewables, energy efficiency, etc. The use of 4IR technologies such as Artificial Intelligence, Machine Learning, and Data Analytics are also discussed. Overlapping technologies, areas of collaboration and synergistic relationships are identified. The unique sustainability analyses provide improved decision-making on technology portfolio management.

Keywords: sustainability, oil& gas, technology portfolio, key performance indicator

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66 Plasma-Assisted Decomposition of Cyclohexane in a Dielectric Barrier Discharge Reactor

Authors: Usman Dahiru, Faisal Saleem, Kui Zhang, Adam Harvey

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Volatile organic compounds (VOCs) are atmospheric contaminants predominantly derived from petroleum spills, solvent usage, agricultural processes, automobile, and chemical processing industries, which can be detrimental to the environment and human health. Environmental problems such as the formation of photochemical smog, organic aerosols, and global warming are associated with VOC emissions. Research showed a clear relationship between VOC emissions and cancer. In recent years, stricter emission regulations, especially in industrialized countries, have been put in place around the world to restrict VOC emissions. Non-thermal plasmas (NTPs) are a promising technology for reducing VOC emissions by converting them into less toxic/environmentally friendly species. The dielectric barrier discharge (DBD) plasma is of interest due to its flexibility, moderate capital cost, and ease of operation under ambient conditions. In this study, a dielectric barrier discharge (DBD) reactor has been developed for the decomposition of cyclohexane (as a VOC model compound) using nitrogen, dry, and humidified air carrier gases. The effect of specific input energy (1.2-3.0 kJ/L), residence time (1.2-2.3 s) and concentration (220-520 ppm) were investigated. It was demonstrated that the removal efficiency of cyclohexane increased with increasing plasma power and residence time. The removal of cyclohexane decreased with increasing cyclohexane inlet concentration at fixed plasma power and residence time. The decomposition products included H₂, CO₂, H₂O, lower hydrocarbons (C₁-C₅) and solid residue. The highest removal efficiency (98.2%) was observed at specific input energy of 3.0 kJ/L and a residence time of 2.3 s in humidified air plasma. The effect of humidity was investigated to determine whether it could reduce the formation of solid residue in the DBD reactor. It was observed that the solid residue completely disappeared in humidified air plasma. Furthermore, the presence of OH radicals due to humidification not only increased the removal efficiency of cyclohexane but also improves product selectivity. This work demonstrates that cyclohexane can be converted to smaller molecules by a dielectric barrier discharge (DBD) non-thermal plasma reactor by varying plasma power (SIE), residence time, reactor configuration, and carrier gas.

Keywords: cyclohexane, dielectric barrier discharge reactor, non-thermal plasma, removal efficiency

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65 Absorption Kinetic and Tensile Mechanical Properties of Swollen Elastomer/Carbon Black Nanocomposites using Typical Solvents

Authors: F. Elhaouzi, H. Lahlali, M. Zaghrioui, I. El Aboudi A. BelfKira, A. Mdarhri

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The effect of physico chemical properties of solvents on the transport process and mechanical properties in elastomeric nano composite materials is reported. The investigated samples are formed by a semi-crystalline ethylene-co-butyl acrylate polymer filled with hard spherical carbon black (CB) nano particles. The swelling behavior was studied by immersion the dried samples in selected solvents at room temperature during 2 days. For this purpose, two chemical compounds methyl derivatives of aromatic hydrocarbons of benzene, i.e. toluene and xylene, are used to search for the mass and molar volume dependence on the absorption kinetics. Mass gain relative to the mass of dry material at specific times was recorded to probe the absorption kinetics. The transport of solvent molecules in these filled elastomeric composites is following a Fickian diffusion mechanism. Additionally, the swelling ratio and diffusivity coefficient deduced from the Fickian law are found to decrease with the CB concentration. These results indicate that the CB nano particles increase the effective path length for diffusion and consequently limit the absorption of the solvent by occupation free volumes in the material. According to physico chemical properties of the two used solvents, it is found that the diffusion is more important for the toluene molecules solvent due to their low values of the molecular weight and volume molar compared to those for the xylene. Differential Scanning Calorimetry (DSC) and X-ray photo electron (XPS) were also used to probe the eventual change in the chemical composition for the swollen samples. Mechanically speaking, the stress-strain curves of uniaxial tensile tests pre- and post- swelling highlight a remarkably decrease of the strength and elongation at break of the swollen samples. This behavior can be attributed to the decrease of the load transfer density between the matrix and the CB in the presence of the solvent. We believe that the results reported in this experimental investigation can be useful for some demanding applications e.g. tires, sealing rubber.

Keywords: nanocomposite, absorption kinetics, mechanical behavior, diffusion, modelling, XPS, DSC

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64 Microfacies and Sedimentary Environment of Potentially Hydrocarbon-Bearing Ordovician and Silurian Deposits of Selected Boreholes in the Baltic Syneclise (NE Poland)

Authors: Katarzyna Sobczak

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Over the last few years extensive research on the Lower Palaeozic of the Baltic region has been carried out, associated with growing interest in the unconventional hydrocarbon resources of the area. The present study contributes to this investigation by providing relevant microfacies analysis of Ordovician and Silurian carbonate and clastic deposits of the Polish part of the Baltic Syneclise, using data from the Kętrzyn IG-1, Henrykowo 1 and Babiak 1 boreholes. The analytical data, encompassing sedimentological, palaeontological, and petrographic indicators enables the interpretation of the sedimentary environments and their control factors. The main microfacies types distinguished within the studied interval are: bioclastic wackestone, bioclastic packstone, carbonate-rich mudstone, marlstone, nodular limestone and bituminous claystone. The Ordovician is represented by redeposited carbonate rocks formed in a relatively high-energy environment (middle shelf setting). The Upper Ordovician-Lower Silurian rocks of the studied basin represent sedimentary succession formed during a distinctive marine transgression. Considering the sedimentological and petrological data from the Silurian, a low-energy sedimentary environment (offshore setting) with intermittent high-energy events (tempestites) can be inferred for the sedimentary basin of NE Poland. Slow sedimentation of carbonate ooze and fine-grained siliciclastic rocks, formed under oxygen-deficient conditions of the seabed, favoured organic matter preservation. The presence of the storm beds suggests an episodic nature of seabed oxygenation. A significant part of the analysed depositional successions shows characteristics indicative of deposition from gravity flows, but lacks evidence of its turbidity origins. There is, however, evidence for storms acting as a mechanism of flow activation. The discussed Ordovician-Silurian transition of depositional environments in the Baltic area fits well to the global environmental changes encompassing the Upper Ordovician and the Lower Silurian.

Keywords: Baltic Syneclise, microfacies analysis, Ordovician, Silurian, unconventional hydrocarbons

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63 Atmospheric Polycyclic Aromatic Hydrocarbons (PAHs) in Rural and Urban of Central Taiwan

Authors: Shih Yu Pan, Pao Chen Hung, Chuan Yao Lin, Charles C.-K. Chou, Yu Chi Lin, Kai Hsien Chi

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This study analyzed 16 atmospheric PAHs species which were controlled by USEPA and IARC. To measure the concentration of PAHs, four rural sampling sites and two urban sampling sites were selected in Central Taiwan during spring and summer. In central Taiwan, the rural sampling stations were located in the downstream of Da-An River, Da-Jang River, Wu River and Chuo-shui River. On the other hand, the urban sampling sites were located in Taichung district and close to the roadside. Ambient air samples of both vapor phase and particle phase of PAHs compounds were collected using high volume sampling trains (Analitica). The sampling media were polyurethane foam (PUF) with XAD2 and quartz fiber filters. Diagnostic ratio, Principal component analysis (PCA), Positive Matrix Factorization (PMF) models were used to evaluate the apportionment of PAHs in the atmosphere and speculate the relative contribution of various emission sources. Because of the high temperature and low wind speed, high PAHs concentration in the atmosphere was observed. The total PAHs concentration, especially in vapor phase, had significant change during summer. During the sampling periods the total PAHs concentration of atmospheric at four rural and two urban sampling sites in spring and summer were 3.70±0.40 ng/m3,3.40±0.63 ng/m3,5.22±1.24 ng/m3,7.23±0.37 ng/m3,7.46±2.36 ng/m3,6.21±0.55 ng/m3 ; 15.0± 0.14 ng/m3,18.8±8.05 ng/m3,20.2±8.58 ng/m3,16.1±3.75 ng/m3,29.8±10.4 ng/m3,35.3±11.8 ng/m3, respectively. In order to identify PAHs sources, we used diagnostic ratio to classify the emission sources. The potential sources were diesel combustion and gasoline combustion in spring and summer, respectively. According to the principal component analysis (PCA), the PC1 and PC2 had 23.8%, 20.4% variance and 21.3%, 17.1% variance in spring and summer, respectively. Especially high molecular weight PAHs (BaP, IND, BghiP, Flu, Phe, Flt, Pyr) were dominated in spring when low molecular weight PAHs (AcPy, Ant, Acp, Flu) because of the dominating high temperatures were dominated in the summer. Analysis by using PMF model found the sources of PAHs in spring were stationary sources (34%), vehicle emissions (24%), coal combustion (23%) and petrochemical fuel gas (19%), while in summer the emission sources were petrochemical fuel gas (34%), the natural environment of volatile organic compounds (29%), coal combustion (19%) and stationary sources (18%).

Keywords: PAHs, source identification, diagnostic ratio, principal component analysis, positive matrix factorization

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62 The Use of Solar Energy for Cold Production

Authors: Nadia Allouache, Mohamed Belmedani

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—It is imperative today to further explore alternatives to fossil fuels by promoting in particular renewable sources such as solar energy to produce cold. It is also important to carefully examine its current state as well as its future prospects in order to identify the best conditions to support its optimal development. Technologies linked to this alternative source fascinate their users because they seem magical in their ability to directly transform solar energy into cooling without resorting to polluting fuels such as those derived from hydrocarbons or other toxic substances. In addition, these not only allow significant savings in electricity, but can also help reduce the costs of electrical energy production when applied on a large scale. In this context, our study aims to analyze the performance of solar adsorption cooling systems by selecting the appropriate pair Adsorbent/Adsorbat. This paper presents a model describing the heat and mass transfer in tubular finned adsorber of solar adsorption refrigerating machine. The modelisation of the solar reactor take into account the heat and mass transfers phenomena. The reactor pressure is assumed to be uniform, the reactive reactor is characterized by an equivalent thermal conductivity and assumed to be at chemical and thermodynamic equilibrium. The numerical model is controlled by heat, mass and sorption equilibrium equations. Under the action of solar radiation, the mixture of adsorbent–adsorbate has a transitory behavior. Effect of key parameters on the adsorbed quantity and on the thermal and solar performances are analyzed and discussed. The results show that, The performances of the system that depends on the incident global irradiance during a whole day depends on the weather conditions. For the used working pairs, the increase of the fins number corresponds to the decreasing of the heat losses towards environmental and the increasing of heat transfer inside the adsorber. The system performances are sensitive to the evaporator and condenser temperatures. For the considered data measured for clear type days of may and july 2023 in Algeria and Tunisia, the performances of the cooling system are very significant in Algeria compared to Tunisia.

Keywords: adsorption, adsorbent-adsorbate pair, finned reactor, numerical modeling, solar energy

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61 Charcoal Traditional Production in Portugal: Contribution to the Quantification of Air Pollutant Emissions

Authors: Cátia Gonçalves, Teresa Nunes, Inês Pina, Ana Vicente, C. Alves, Felix Charvet, Daniel Neves, A. Matos

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The production of charcoal relies on rudimentary technologies using traditional brick kilns. Charcoal is produced under pyrolysis conditions: breaking down the chemical structure of biomass under high temperature in the absence of air. The amount of the pyrolysis products (charcoal, pyroligneous extract, and flue gas) depends on various parameters, including temperature, time, pressure, kiln design, and wood characteristics like the moisture content. This activity is recognized for its inefficiency and high pollution levels, but it is poorly characterized. This activity is widely distributed and is a vital economic activity in certain regions of Portugal, playing a relevant role in the management of woody residues. The location of the units establishes the biomass used for charcoal production. The Portalegre district, in the Alto Alentejo region (Portugal), is a good example, essentially with rural characteristics, with a predominant farming, agricultural, and forestry profile, and with a significant charcoal production activity. In this district, a recent inventory identifies almost 50 charcoal production units, equivalent to more than 450 kilns, of which 80% appear to be in operation. A field campaign was designed with the objective of determining the composition of the emissions released during a charcoal production cycle. A total of 30 samples of particulate matter and 20 gas samples in Tedlar bags were collected. Particulate and gas samplings were performed in parallel, 2 in the morning and 2 in the afternoon, alternating the inlet heads (PM₁₀ and PM₂.₅), in the particulate sampler. The gas and particulate samples were collected in the plume as close as the emission chimney point. The biomass (dry basis) used in the carbonization process was a mixture of cork oak (77 wt.%), holm oak (7 wt.%), stumps (11 wt.%), and charred wood (5 wt.%) from previous carbonization processes. A cylindrical batch kiln (80 m³) with 4.5 m diameter and 5 m of height was used in this study. The composition of the gases was determined by gas chromatography, while the particulate samples (PM₁₀, PM₂.₅) were subjected to different analytical techniques (thermo-optical transmission technique, ion chromatography, HPAE-PAD, and GC-MS after solvent extraction) after prior gravimetric determination, to study their organic and inorganic constituents. The charcoal production cycle presents widely varying operating conditions, which will be reflected in the composition of gases and particles produced and emitted throughout the process. The concentration of PM₁₀ and PM₂.₅ in the plume was calculated, ranging between 0.003 and 0.293 g m⁻³, and 0.004 and 0.292 g m⁻³, respectively. Total carbon, inorganic ions, and sugars account, in average, for PM10 and PM₂.₅, 65 % and 56 %, 2.8 % and 2.3 %, 1.27 %, and 1.21 %, respectively. The organic fraction studied until now includes more than 30 aliphatic compounds and 20 PAHs. The emission factors of particulate matter to produce charcoal in the traditional kiln were 33 g/kg (wooddb) and 27 g/kg (wooddb) for PM₁₀ and PM₂.₅, respectively. With the data obtained in this study, it is possible to fill the lack of information about the environmental impact of the traditional charcoal production in Portugal. Acknowledgment: Authors thanks to FCT – Portuguese Science Foundation, I.P. and to Ministry of Science, Technology and Higher Education of Portugal for financial support within the scope of the project CHARCLEAN (PCIF/GVB/0179/2017) and CESAM (UIDP/50017/2020 + UIDB/50017/2020).

Keywords: brick kilns, charcoal, emission factors, PAHs, total carbon

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60 Expanded Polyurethane Foams and Waterborne-Polyurethanes from Vegetable Oils

Authors: A.Cifarelli, L. Boggioni, F. Bertini, L. Magon, M. Pitalieri, S. Losio

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Nowadays, the growing environmental awareness and the dwindling of fossil resources stimulate the polyurethane (PU) industry towards renewable polymers with low carbon footprint to replace the feed stocks from petroleum sources. The main challenge in this field consists in replacing high-performance products from fossil-fuel with novel synthetic polymers derived from 'green monomers'. The bio-polyols from plant oils have attracted significant industrial interest and major attention in scientific research due to their availability and biodegradability. Triglycerides rich in unsaturated fatty acids, such as soybean oil (SBO) and linseed oil (ELO), are particularly interesting because their structures and functionalities are tunable by chemical modification in order to obtain polymeric materials with expected final properties. Unfortunately, their use is still limited for processing or performance problems because a high functionality, as well as OH number of the polyols will result in an increase in cross-linking densities of the resulting PUs. The main aim of this study is to evaluate soy and linseed-based polyols as precursors to prepare prepolymers for the production of polyurethane foams (PUFs) or waterborne-polyurethanes (WPU) used as coatings. An effective reaction route is employed for its simplicity and economic impact. Indeed, bio-polyols were synthesized by a two-step method: epoxidation of the double bonds in vegetable oils and solvent-free ring-opening reaction of the oxirane with organic acids. No organic solvents have been used. Acids with different moieties (aliphatic or aromatics) and different length of hydrocarbon backbones can be used to customize polyols with different functionalities. The ring-opening reaction requires a fine tuning of the experimental conditions (time, temperature, molar ratio of carboxylic acid and epoxy group) to control the acidity value of end-product as well as the amount of residual starting materials. Besides, a Lewis base catalyst is used to favor the ring opening reaction of internal epoxy groups of the epoxidized oil and minimize the formation of cross-linked structures in order to achieve less viscous and more processable polyols with narrower polydispersity indices (molecular weight lower than 2000 g/mol⁻¹). The functionality of optimized polyols is tuned from 2 to 4 per molecule. The obtained polyols are characterized by means of GPC, NMR (¹H, ¹³C) and FT-IR spectroscopy to evaluate molecular masses, molecular mass distributions, microstructures and linkage pathways. Several polyurethane foams have been prepared by prepolymer method blending conventional synthetic polyols with new bio-polyols from soybean and linseed oils without using organic solvents. The compatibility of such bio-polyols with commercial polyols and diisocyanates is demonstrated. The influence of the bio-polyols on the foam morphology (cellular structure, interconnectivity), density, mechanical and thermal properties has been studied. Moreover, bio-based WPUs have been synthesized by well-established processing technology. In this synthesis, a portion of commercial polyols is substituted by the new bio-polyols and the properties of the coatings on leather substrates have been evaluated to determine coating hardness, abrasion resistance, impact resistance, gloss, chemical resistance, flammability, durability, and adhesive strength.

Keywords: bio-polyols, polyurethane foams, solvent free synthesis, waterborne-polyurethanes

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59 Effect of Water Addition on Catalytic Activity for CO2 Purification from Oxyfuel Combustion

Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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58 Desulphurization of Waste Tire Pyrolytic Oil (TPO) Using Photodegradation and Adsorption Techniques

Authors: Moshe Mello, Hilary Rutto, Tumisang Seodigeng

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The nature of tires makes them extremely challenging to recycle due to the available chemically cross-linked polymer and, therefore, they are neither fusible nor soluble and, consequently, cannot be remolded into other shapes without serious degradation. Open dumping of tires pollutes the soil, contaminates underground water and provides ideal breeding grounds for disease carrying vermins. The thermal decomposition of tires by pyrolysis produce char, gases and oil. The composition of oils derived from waste tires has common properties to commercial diesel fuel. The problem associated with the light oil derived from pyrolysis of waste tires is that it has a high sulfur content (> 1.0 wt.%) and therefore emits harmful sulfur oxide (SOx) gases to the atmosphere when combusted in diesel engines. Desulphurization of TPO is necessary due to the increasing stringent environmental regulations worldwide. Hydrodesulphurization (HDS) is the commonly practiced technique for the removal of sulfur species in liquid hydrocarbons. However, the HDS technique fails in the presence of complex sulfur species such as Dibenzothiopene (DBT) present in TPO. This study aims to investigate the viability of photodegradation (Photocatalytic oxidative desulphurization) and adsorptive desulphurization technologies for efficient removal of complex and non-complex sulfur species in TPO. This study focuses on optimizing the cleaning (removal of impurities and asphaltenes) process by varying process parameters; temperature, stirring speed, acid/oil ratio and time. The treated TPO will then be sent for vacuum distillation to attain the desired diesel like fuel. The effect of temperature, pressure and time will be determined for vacuum distillation of both raw TPO and the acid treated oil for comparison purposes. Polycyclic sulfides present in the distilled (diesel like) light oil will be oxidized dominantly to the corresponding sulfoxides and sulfone via a photo-catalyzed system using TiO2 as a catalyst and hydrogen peroxide as an oxidizing agent and finally acetonitrile will be used as an extraction solvent. Adsorptive desulphurization will be used to adsorb traces of sulfurous compounds which remained during photocatalytic desulphurization step. This desulphurization convoy is expected to give high desulphurization efficiency with reasonable oil recovery.

Keywords: adsorption, asphaltenes, photocatalytic oxidation, pyrolysis

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57 An Overview of the Porosity Classification in Carbonate Reservoirs and Their Challenges: An Example of Macro-Microporosity Classification from Offshore Miocene Carbonate in Central Luconia, Malaysia

Authors: Hammad T. Janjuhah, Josep Sanjuan, Mohamed K. Salah

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Biological and chemical activities in carbonates are responsible for the complexity of the pore system. Primary porosity is generally of natural origin while secondary porosity is subject to chemical reactivity through diagenetic processes. To understand the integrated part of hydrocarbon exploration, it is necessary to understand the carbonate pore system. However, the current porosity classification scheme is limited to adequately predict the petrophysical properties of different reservoirs having various origins and depositional environments. Rock classification provides a descriptive method for explaining the lithofacies but makes no significant contribution to the application of porosity and permeability (poro-perm) correlation. The Central Luconia carbonate system (Malaysia) represents a good example of pore complexity (in terms of nature and origin) mainly related to diagenetic processes which have altered the original reservoir. For quantitative analysis, 32 high-resolution images of each thin section were taken using transmitted light microscopy. The quantification of grains, matrix, cement, and macroporosity (pore types) was achieved using a petrographic analysis of thin sections and FESEM images. The point counting technique was used to estimate the amount of macroporosity from thin section, which was then subtracted from the total porosity to derive the microporosity. The quantitative observation of thin sections revealed that the mouldic porosity (macroporosity) is the dominant porosity type present, whereas the microporosity seems to correspond to a sum of 40 to 50% of the total porosity. It has been proven that these Miocene carbonates contain a significant amount of microporosity, which significantly complicates the estimation and production of hydrocarbons. Neglecting its impact can increase uncertainty about estimating hydrocarbon reserves. Due to the diversity of geological parameters, the application of existing porosity classifications does not allow a better understanding of the poro-perm relationship. However, the classification can be improved by including the pore types and pore structures where they can be divided into macro- and microporosity. Such studies of microporosity identification/classification represent now a major concern in limestone reservoirs around the world.

Keywords: overview of porosity classification, reservoir characterization, microporosity, carbonate reservoir

Procedia PDF Downloads 154
56 Advanced Technology for Natural Gas Liquids (NGL) Recovery Using Residue Gas Split

Authors: Riddhiman Sherlekar, Umang Paladia, Rachit Desai, Yash Patel

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The competitive scenario of the oil and gas market is a challenge for today’s plant designers to achieve designs that meet client expectations with shrinking budgets, safety requirements, and operating flexibility. Natural Gas Liquids have three main industrial uses. They can be used as fuels, or as petrochemical feedstock or as refinery blends that can be further processed and sold as straight run cuts, such as naphtha, kerosene and gas oil. NGL extraction is not a chemical reaction. It involves the separation of heavier hydrocarbons from the main gas stream through pressure as temperature reduction, which depending upon the degree of NGL extraction may involve cryogenic process. Previous technologies i.e. short cycle dry desiccant absorption, Joule-Thompson or Low temperature refrigeration, lean oil absorption have been giving results of only 40 to 45% ethane recoveries, which were unsatisfying depending upon the current scenario of down turn market. Here new technology has been suggested for boosting up the recoveries of ethane+ up to 95% and up to 99% for propane+ components. Cryogenic plants provide reboiling to demethanizers by using part of inlet feed gas, or inlet feed split. If the two stream temperatures are not similar, there is lost work in the mixing operation unless the designer has access to some proprietary design. The concept introduced in this process consists of reboiling the demethanizer with the residue gas, or residue gas split. The innovation of this process is that it does not use the typical inlet gas feed split type of flow arrangement to reboil the demethanizer or deethanizer column, but instead uses an open heat pump scheme to that effect. The residue gas compressor provides the heat pump effect. The heat pump stream is then further cooled and entered in the top section of the column as a cold reflux. Because of the nature of this design, this process offers the opportunity to operate at full ethane rejection or recovery. The scheme is also very adaptable to revamp existing facilities. This advancement can be proven not only in enhancing the results but also provides operational flexibility, optimize heat exchange, introduces equipment cost reduction, opens a future for the innovative designs while keeping execution costs low.

Keywords: deethanizer, demethanizer, residue gas, NGL

Procedia PDF Downloads 265
55 Seasonal Variations, Environmental Parameters, and Standing Crop Assessment of Benthic Foraminifera in Western Bahrain, Arabian Gulf

Authors: Muhammad Arslan, Michael A. Kaminski, Bassam S. Tawabini, Fabrizio Frontalini

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We conducted a survey of living benthic foraminifera in a relatively unpolluted site of Bahrain in the Arabian Gulf, with the aim of determining the seasonal variability in their populations, as well as various environmental parameters that affect their distribution. The maximum standing crop was observed during winter, with highest population of rotaliids, followed by a peak in miliolids. The highest population is attributed to an increasing number juveniles observed along the depth transect. A strong correlation between sediment grain size and the foraminiferal population indicates that juveniles were most abundant on coarser sandy substrate and less abundant on fine substrate. In spring, the total living population decreased, and lowest values are observed in the summer. The population started to increase again in the autumn with highest juveniles/adult ratios. Moreover, results of relative abundance and species consistency show that Ammonia is found to be consistent from the shallowest to the deepest station, whereas miliolids start appearing in the deeper stations. The average numbers of Peneroplis and Elphidium also increases along the depth transect. Environmental characterization reveals that although the site is subjected to eutrophication caused by nitrates and sulfates, pollution caused by hydrocarbons and heavy metals is not significant. The assessment of 63 heavy metals showed that none of the metals had concentrations that exceed internationally accepted norms [the devised level of Effect Range-Low], with the exception of strontium. The lack of a significant environmental effect of heavy metals is confirmed by a Foraminiferal Deformities Index value of less than 2%. Likewise, no hydrocarbon contamination was detected in the water or sediment samples. Lastly, observations of cytoplasmic streaming and pseudopodial activity in Petri dishes suggest that the foraminiferal population is not stressed. We conclude that the site in Bahrain is not yet adversely affected by human development, and therefore can provide baseline information for future comparison and assessment of foraminiferal assemblages in contaminated zones of the Arabian Gulf.

Keywords: Arabian Gulf, benthic foraminifera, standing crop, Western Bahrain

Procedia PDF Downloads 643
54 GIS Technology for Environmentally Polluted Sites with Innovative Process to Improve the Quality and Assesses the Environmental Impact Assessment (EIA)

Authors: Hamad Almebayedh, Chuxia Lin, Yu wang

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The environmental impact assessment (EIA) must be improved, assessed, and quality checked for human and environmental health and safety. Soil contamination is expanding, and sites and soil remediation activities proceeding around the word which simplifies the answer “quality soil characterization” will lead to “quality EIA” to illuminate the contamination level and extent and reveal the unknown for the way forward to remediate, countifying, containing, minimizing and eliminating the environmental damage. Spatial interpolation methods play a significant role in decision making, planning remediation strategies, environmental management, and risk assessment, as it provides essential elements towards site characterization, which need to be informed into the EIA. The Innovative 3D soil mapping and soil characterization technology presented in this research paper reveal the unknown information and the extent of the contaminated soil in specific and enhance soil characterization information in general which will be reflected in improving the information provided in developing the EIA related to specific sites. The foremost aims of this research paper are to present novel 3D mapping technology to quality and cost-effectively characterize and estimate the distribution of key soil characteristics in contaminated sites and develop Innovative process/procedure “assessment measures” for EIA quality and assessment. The contaminated site and field investigation was conducted by innovative 3D mapping technology to characterize the composition of petroleum hydrocarbons contaminated soils in a decommissioned oilfield waste pit in Kuwait. The results show the depth and extent of the contamination, which has been interred into a developed assessment process and procedure for the EIA quality review checklist to enhance the EIA and drive remediation and risk assessment strategies. We have concluded that to minimize the possible adverse environmental impacts on the investigated site in Kuwait, the soil-capping approach may be sufficient and may represent a cost-effective management option as the environmental risk from the contaminated soils is considered to be relatively low. This research paper adopts a multi-method approach involving reviewing the existing literature related to the research area, case studies, and computer simulation.

Keywords: quality EIA, spatial interpolation, soil characterization, contaminated site

Procedia PDF Downloads 88
53 Analysis of Brownfield Soil Contamination Using Local Government Planning Data

Authors: Emma E. Hellawell, Susan J. Hughes

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BBrownfield sites are currently being redeveloped for residential use. Information on soil contamination on these former industrial sites is collected as part of the planning process by the local government. This research project analyses this untapped resource of environmental data, using site investigation data submitted to a local Borough Council, in Surrey, UK. Over 150 site investigation reports were collected and interrogated to extract relevant information. This study involved three phases. Phase 1 was the development of a database for soil contamination information from local government reports. This database contained information on the source, history, and quality of the data together with the chemical information on the soil that was sampled. Phase 2 involved obtaining site investigation reports for development within the study area and extracting the required information for the database. Phase 3 was the data analysis and interpretation of key contaminants to evaluate typical levels of contaminants, their distribution within the study area, and relating these results to current guideline levels of risk for future site users. Preliminary results for a pilot study using a sample of the dataset have been obtained. This pilot study showed there is some inconsistency in the quality of the reports and measured data, and careful interpretation of the data is required. Analysis of the information has found high levels of lead in shallow soil samples, with mean and median levels exceeding the current guidance for residential use. The data also showed elevated (but below guidance) levels of potentially carcinogenic polyaromatic hydrocarbons. Of particular concern from the data was the high detection rate for asbestos fibers. These were found at low concentrations in 25% of the soil samples tested (however, the sample set was small). Contamination levels of the remaining chemicals tested were all below the guidance level for residential site use. These preliminary pilot study results will be expanded, and results for the whole local government area will be presented at the conference. The pilot study has demonstrated the potential for this extensive dataset to provide greater information on local contamination levels. This can help inform regulators and developers and lead to more targeted site investigations, improving risk assessments, and brownfield development.

Keywords: Brownfield development, contaminated land, local government planning data, site investigation

Procedia PDF Downloads 138
52 Syngas From Polypropylene Gasification in a Fluidized Bed

Authors: Sergio Rapagnà, Alessandro Antonio Papa, Armando Vitale, Andre Di Carlo

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In recent years the world population has enormously increased the use of plastic products for their living needs, in particular for transporting and storing consumer goods such as food and beverage. Plastics are widely used in the automotive industry, in construction of electronic equipment, clothing and home furnishings. Over the last 70 years, the annual production of plastic products has increased from 2 million tons to 460 million tons. About 20% of the last quantity is mismanaged as waste. The consequence of this mismanagement is the release of plastic waste into the terrestrial and marine environments which represents a danger to human health and the ecosystem. Recycling all plastics is difficult because they are often made with mixtures of polymers that are incompatible with each other and contain different additives. The products obtained are always of lower quality and after two/three recycling cycles they must be eliminated either by thermal treatment to produce heat or disposed of in landfill. An alternative to these current solutions is to obtain a mixture of gases rich in H₂, CO and CO₂ suitable for being profitably used for the production of chemicals with consequent savings fossil sources. Obtaining a hydrogen-rich syngas can be achieved by gasification process using the fluidized bed reactor, in presence of steam as the fluidization medium. The fluidized bed reactor allows the gasification process of plastics to be carried out at a constant temperature and allows the use of different plastics with different compositions and different grain sizes. Furthermore, during the gasification process the use of steam increase the gasification of char produced by the first pyrolysis/devolatilization process of the plastic particles. The bed inventory can be made with particles having catalytic properties such as olivine, capable to catalyse the steam reforming reactions of heavy hydrocarbons normally called tars, with a consequent increase in the quantity of gases produced. The plant is composed of a fluidized bed reactor made of AISI 310 steel, having an internal diameter of 0.1 m, containing 3 kg of olivine particles as a bed inventory. The reactor is externally heated by an oven up to 1000 °C. The hot producer gases that exit the reactor, after being cooled, are quantified using a mass flow meter. Gas analyzers are present to measure instantly the volumetric composition of H₂, CO, CO₂, CH₄ and NH₃. At the conference, the results obtained from the continuous gasification of polypropylene (PP) particles in a steam atmosphere at temperatures of 840-860 °C will be presented.

Keywords: gasification, fluidized bed, hydrogen, olivine, polypropyle

Procedia PDF Downloads 27
51 Co-Gasification of Petroleum Waste and Waste Tires: A Numerical and CFD Study

Authors: Thomas Arink, Isam Janajreh

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The petroleum industry generates significant amounts of waste in the form of drill cuttings, contaminated soil and oily sludge. Drill cuttings are a product of the off-shore drilling rigs, containing wet soil and total petroleum hydrocarbons (TPH). Contaminated soil comes from different on-shore sites and also contains TPH. The oily sludge is mainly residue or tank bottom sludge from storage tanks. The two main treatment methods currently used are incineration and thermal desorption (TD). Thermal desorption is a method where the waste material is heated to 450ºC in an anaerobic environment to release volatiles, the condensed volatiles can be used as a liquid fuel. For the thermal desorption unit dry contaminated soil is mixed with moist drill cuttings to generate a suitable mixture. By thermo gravimetric analysis (TGA) of the TD feedstock it was found that less than 50% of the TPH are released, the discharged material is stored in landfill. This study proposes co-gasification of petroleum waste with waste tires as an alternative to thermal desorption. Co-gasification with a high-calorific material is necessary since the petroleum waste consists of more than 60 wt% ash (soil/sand), causing its calorific value to be too low for gasification. Since the gasification process occurs at 900ºC and higher, close to 100% of the TPH can be released, according to the TGA. This work consists of three parts: 1. a mathematical gasification model, 2. a reactive flow CFD model and 3. experimental work on a drop tube reactor. Extensive material characterization was done by means of proximate analysis (TGA), ultimate analysis (CHNOS flash analysis) and calorific value measurements (Bomb calorimeter) for the input parameters of the mathematical and CFD model. The mathematical model is a zero dimensional model based on Gibbs energy minimization together with Lagrange multiplier; it is used to find the product species composition (molar fractions of CO, H2, CH4 etc.) for different tire/petroleum feedstock mixtures and equivalence ratios. The results of the mathematical model act as a reference for the CFD model of the drop-tube reactor. With the CFD model the efficiency and product species composition can be predicted for different mixtures and particle sizes. Finally both models are verified by experiments on a drop tube reactor (1540 mm long, 66 mm inner diameter, 1400 K maximum temperature).

Keywords: computational fluid dynamics (CFD), drop tube reactor, gasification, Gibbs energy minimization, petroleum waste, waste tires

Procedia PDF Downloads 520
50 Abatement of NO by CO on Pd Catalysts: Influence of the Support in Oxyfuel Combustion Conditions

Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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The CO2 emitted from anthropic activities is perceived as a constraint in industrial activity due to taxes, stringent environmental regulations, impact on global warming… To limit these CO2 emissions, reuse of CO2 represents a promising alternative, with important applications in chemical industry and for power generation. However, CO2 valorization process requires a gas as pure as possible Oxyfuel-combustion that enables obtaining a CO2 rich stream, with water vapor (10%) is then interesting. Nevertheless to decrease the amount of the by-products found with the CO2 (especially CO and NOx which are harmful to the environment) a catalytic treatment must be applied. Nowadays three-way catalysts are well-developed material for simultaneous conversion of unburned hydrocarbons, carbon monoxide (CO) and nitrogen oxides (NOx). The use of Pd attracted considerable attention on the basis of economic factors (the high cost and scarcity of Pt and Rh). This explains the large number of studies concerning the CO-NO reaction on Pd in the recent years. In the present study, we will compare a series of Pd materials supported on different oxides for CO2 purification from the oxyfuel combustion system, by reducing NO with CO in an oxidizing environment containing CO2 rich stream and presence of 8.2% of water. Al2O3, CeO2, MgO, SiO2 and TiO2 were used as support materials of the catalysts. 1wt% Pd/Support catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2]. The obtained samples were subsequently characterized by H2 chemisorption, BET surface area and TEM. Finally, their catalytic performances were evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200mL.min−1, in the same GHSV. The catalytic performance of the Pd catalysts for CO2 purification revealed that: -The support material has a strong influence on the catalytic activity of 1wt.% Pd supported catalysts. depending of the nature of support, the Pd-based catalysts activity changes. -The highest reduction of NO with CO is obtained in the following ranking: TiO2>CeO2>Al2O3. -The supports SiO2 and MgO should be avoided for this reaction, -Total oxidation of CO occurred over different materials, -CO2 purification can reach 97%, -The presence of H2O has a positive effect on the NO reduction due to the production of the reductant H2 from WGS reaction H2O+CO → H2+CO2

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis, oxyfuel combustion

Procedia PDF Downloads 255
49 The Effect of Organic Matter Maturation and Porosity Evolution on Methane Storage Potential in Shale-Gas Reservoirs

Authors: T. Topór, A. Derkowski, P. Ziemiański

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Formation of organic matter (OM)-hosted nanopores upon thermal maturation are one of the key factor controlling methane storage potential in unconventional shale-gas reservoirs. In this study, the subcritical CO₂ and N₂ gas adsorption measurements combined with scanning electron microscopy and supercritical methane adsorption have been used to characterize pore system and methane storage potential in black shales from the Baltic Basin (Poland). The samples were collected from a virtually equivalent Llandovery strata across the basin and represent a complete digenetic sequence, from thermally immature to overmature. The results demonstrate that the thermal maturation is a dominant mechanism controlling the formation of OM micro- and mesopores in the Baltic Basin shales. The formation of micro- and mesopores occurs in the oil window (vitrinite reflectance; leavedVR; ~0.5-0.9%) as a result of oil expulsion from kerogenleft OM highly porous. The generated hydrocarbons then turn into solid bitumen causing pore blocking and substantial decrease in micro- and mesopore volume in late-mature shales (VR ~0.9-1.2%). Both micro- and mesopores are regenerated in a middle of the catagenesis range (VR 1.4-1.9%) due to secondary cracking of OM and gas formation. The micropore volume in investigated shales is almost exclusively controlled by the OM content. The contribution of clay minerals to micropore volume is insignificant and masked by a strong contribution from OM. Methane adsorption capacity in the Baltic Basin shales is predominantly controlled by microporous OM with pores < 1.5 nm. The mesopore volume (2-50 nm) and mesopore surface area have no effect on methane sorption behavior. The adsorbed methane density equivalent, calculated as absolute methane adsorption divided by micropore volume, reviled a decrease of the methane loading potential in micropores with increasing maturity. The highest methane loading potential in micropores is observed for OM before metagenesis (VR < 2%), where the adsorbed methane density equivalent is greater than the density of liquid methane. This implies that, in addition to physical adsorption, absorption of methane in OM may occur before metagenesis. After OM content reduction using NaOCl solution methane adoption capacity substantially decreases, suggesting significantly greater adsorption potential for OM microstructure than for the clay minerals matrix.

Keywords: maturation, methane sorption, organic matter, porosity, shales

Procedia PDF Downloads 236
48 The Challenges of Well Integrity on Plug and Abandoned Wells for Offshore Co₂ Storage Site Containment

Authors: Siti Noor Syahirah Mohd Sabri

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The oil and gas industry is committed to net zero carbon emissions because the consequences of climate change could be catastrophic unless responded to very soon. One way of reducing CO₂ emissions is to inject it into a depleted reservoir buried underground. This greenhouse gas reduction technique significantly reduces CO₂ released into the atmosphere. In general, depleted oil and gas reservoirs provide readily available sites for the storage of CO₂ in offshore areas. This is mainly due to the hydrocarbons have been optimally produced and the existence of voids for effective CO₂ storage. Hence, make it a good candidate for a CO₂ well injector location. Geological storage sites are often evaluated in terms of capacity, injectivity and containment. Leakage through the cap rock or existing well is the main concern in the depleted fields. In order to develop these fields as CO₂ storage sites, the long-term integrity of wells drilled in these oil & gas fields must be ascertained to ensure good CO₂ containment. Well, integrity is often defined as the ability to contain fluids without significant leakage through the project lifecycle. Most plugged and abandoned (P & A) wells in Peninsular Malaysia have drilled 20 – 30 years ago and were not designed to withstand downhole conditions having >50%vol CO₂ and CO₂/H₂O mixture. In addition, Corrosive-Resistant Alloy (CRA) tubular and CO₂-resistant cement was not used during good construction. The reservoir pressure and temperature conditions may have further degraded the material strength and elevated the corrosion rate. Understanding all the uncertainties that may have affected cement-casing bonds, such as the quality of cement behind the casing, subsidence effect, corrosion rate, etc., is the first step toward well integrity evaluation. Secondly, proper quantification of all the uncertainties involved needs to be done to ensure long-term underground storage objectives of CO₂ are achieved. This paper will discuss challenges associated with estimating the performance of well barrier elements in existing P&A wells. Risk ranking of the existing P&A wells is to be carried out in order to ensure the integrity of the storage site is maintained for long-term CO₂ storage. High-risk existing P&A wells are to be re-entered to restore good integrity and to reduce future leakage that may happen. In addition, the requirement to design a fit-for-purpose monitoring and mitigation technology package for potential CO₂ leakage/seepage in the marine environment will be discussed accordingly. The holistic approach will ensure that the integrity is maintained, and CO₂ is contained underground for years to come.

Keywords: CCUS, well integrity, co₂ storage, offshore

Procedia PDF Downloads 90
47 Chemical Composition of Volatiles Emitted from Ziziphus jujuba Miller Collected during Different Growth Stages

Authors: Rose Vanessa Bandeira Reidel, Bernardo Melai, Pier Luigi Cioni, Luisa Pistelli

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Ziziphus jujuba Miller is a common species of the Ziziphus genus (Rhamnaceae family) native to the tropics and subtropics known for its edible fruits, fresh consumed or used in healthy food, as flavoring and sweetener. Many phytochemicals and biological activities are described for this species. In this work, the aroma profiles emitted in vivo by whole fresh organs (leaf, bud flower, flower, green and red fruits) were analyzed separately by mean of solid phase micro-extraction (SPME) coupled with gas chromatography mass spectrometry (GC-MS). The emitted volatiles from different plant parts were analysed using Supelco SPME device coated with polydimethylsiloxane (PDMS, 100µm). Fresh plant material was introduced separately into a glass conical flask and allowed to equilibrate for 20 min. After the equilibration time, the fibre was exposed to the headspace for 15 min at room temperature, the fibre was re-inserted into the needle and transferred to the injector of the CG and CG-MS system, where the fibre was desorbed. All the data were submitted to multivariate statistical analysis, evidencing many differences amongst the selected plant parts and their developmental stages. A total of 144 compounds were identified corresponding to 94.6-99.4% of the whole aroma profile of jujube samples. Sesquiterpene hydrocarbons were the main chemical class of compounds in leaves also present in similar percentage in flowers and bud flowers where (E, E)-α-farnesene was the main constituent in all cited plant parts. This behavior can be due to a protection mechanism against pathogens and herbivores as well as resistance to abiotic factors. The aroma of green fruits was characterized by high amount of perillene while the red fruits release a volatile blend mainly constituted by different monoterpenes. The terpenoid emission of flesh fruits has important function in the interaction with animals including attraction of seed dispersers and it is related to a good quality of fruits. This study provides for the first time the chemical composition of the volatile emission from different Ziziphus jujuba organs. The SPME analyses of the collected samples showed different patterns of emission and can contribute to understand their ecological interactions and fruit production management.

Keywords: Rhamnaceae, aroma profile, jujube organs, HS-SPME, GC-MS

Procedia PDF Downloads 256
46 Geochemical Study of Natural Bitumen, Condensate and Gas Seeps from Sousse Area, Central Tunisia

Authors: Belhaj Mohamed, M. Saidi, N. Boucherab, N. Ouertani, I. Bouazizi, M. Ben Jrad

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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 (GC-MS), capillary GC with flame-ionization detection, Compund 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.

Keywords: biomarkers, oil and gas seeps, organic geochemistry, source rock

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45 Optimizing Hydrogen Production from Biomass Pyro-Gasification in a Multi-Staged Fluidized Bed Reactor

Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

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In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: multi-staged fluidized bed reactor, pyro-gasification, steam methane reforming, water-gas shift

Procedia PDF Downloads 138
44 Phytoremediation of Hydrocarbon-Polluted Soils: Assess the Potentialities of Six Tropical Plant Species

Authors: Pulcherie Matsodoum Nguemte, Adrien Wanko Ngnien, Guy Valerie Djumyom Wafo, Ives Magloire Kengne Noumsi, Pierre Francois Djocgoue

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The identification of plant species with the capacity to grow on hydrocarbon-polluted soils is an essential step for phytoremediation. In view of developing phytoremediation in Cameroon, floristic surveys have been conducted in 4 cities (Douala, Yaounde, Limbe, and Kribi). In each city, 13 hydrocarbon-polluted, as well as unpolluted sites (control), have been investigated using quadrat method. 106 species belonging to 76 genera and 30 families have been identified on hydrocarbon-polluted sites, unlike the control sites where floristic diversity was much higher (166 species contained in 125 genera and 50 families). Poaceae, Cyperaceae, Asteraceae and Amaranthaceae have higher taxonomic richness on polluted sites (16, 15,10 and 8 taxa, respectively). Shannon diversity index of the hydrocarbon-polluted sites (1.6 to 2.7 bits/ind.) were significantly lower than the control sites (2.7 to 3.2 bits/ind.). Based on a relative frequency > 10% and abundance > 7%, this study highlights more than ten plants predisposed to be effective in the cleaning-up attempts of soils contaminated by hydrocarbons. Based on the floristic indicators, 6 species (Eleusine indica (L.) Gaertn., Cynodon dactylon (L.) Pers., Alternanthera sessilis (L.) R. Br. ex DC †, Commelinpa benghalensis L., Cleome ciliata Schum. & Thonn. and Asystasia gangetica (L.) T. Anderson) were selected for a study to determine their capacity to remediate a soil contaminated with fuel oil (82.5 ml/ kg of soil). The experiments lasting 150 days takes into account three modalities - Tn: uncontaminated soils planted (6) To contaminated soils unplanted (3) and Tp: contaminated soil planted (18) – randomized arranged. 3 on 6 species (Eleusine indica, Cynodon dactylon, and Alternanthera sessilis) survived the climatic and soil conditions. E. indica presents a significantly higher growth rate for density and leaf area while C. dactylon had a significantly higher growth rate for stem size and leaf numbers. A. sessilis showed stunted growth and development throughout the experimental period. The species Eleusine indica (L.) Gaertn. and Cynodon dactylon (L.) Pers. can be qualified as polluo-tolerant plant species; polluo-tolerance being the ability of a species to survive and develop in the midst subject to extreme physical and chemical disturbances.

Keywords: Cameroon, cleaning-up, floristic surveys, phytoremediation

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43 Experimental Investigation of Hydrogen Addition in the Intake Air of Compressed Engines Running on Biodiesel Blend

Authors: Hendrick Maxil Zárate Rocha, Ricardo da Silva Pereira, Manoel Fernandes Martins Nogueira, Carlos R. Pereira Belchior, Maria Emilia de Lima Tostes

Abstract:

This study investigates experimentally the effects of hydrogen addition in the intake manifold of a diesel generator operating with a 7% biodiesel-diesel oil blend (B7). An experimental apparatus setup was used to conduct performance and emissions tests in a single cylinder, air cooled diesel engine. This setup consisted of a generator set connected to a wirewound resistor load bank that was used to vary engine load. In addition, a flowmeter was used to determine hydrogen volumetric flowrate and a digital anemometer coupled with an air box to measure air flowrate. Furthermore, a digital precision electronic scale was used to measure engine fuel consumption and a gas analyzer was used to determine exhaust gas composition and exhaust gas temperature. A thermopar was installed near the exhaust collection to measure cylinder temperature. In-cylinder pressure was measured using an AVL Indumicro data acquisition system with a piezoelectric pressure sensor. An AVL optical encoder was installed in the crankshaft and synchronized with in-cylinder pressure in real time. The experimental procedure consisted of injecting hydrogen into the engine intake manifold at different mass concentrations of 2,6,8 and 10% of total fuel mass (B7 + hydrogen), which represented energy fractions of 5,15, 20 and 24% of total fuel energy respectively. Due to hydrogen addition, the total amount of fuel energy introduced increased and the generators fuel injection governor prevented any increases of engine speed. Several conclusions can be stated from the test results. A reduction in specific fuel consumption as a function of hydrogen concentration increase was noted. Likewise, carbon dioxide emissions (CO2), carbon monoxide (CO) and unburned hydrocarbons (HC) decreased as hydrogen concentration increased. On the other hand, nitrogen oxides emissions (NOx) increased due to average temperatures inside the cylinder being higher. There was also an increase in peak cylinder pressure and heat release rate inside the cylinder, since the fuel ignition delay was smaller due to hydrogen content increase. All this indicates that hydrogen promotes faster combustion and higher heat release rates and can be an important additive to all kind of fuels used in diesel generators.

Keywords: diesel engine, hydrogen, dual fuel, combustion analysis, performance, emissions

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42 Evaluation of Low-Global Warming Potential Refrigerants in Vapor Compression Heat Pumps

Authors: Hamed Jafargholi

Abstract:

Global warming presents an immense environmental risk, causing detrimental impacts on ecological systems and putting coastal areas at risk. Implementing efficient measures to minimize greenhouse gas emissions and the use of fossil fuels is essential to reducing global warming. Vapor compression heat pumps provide a practical method for harnessing energy from waste heat sources and reducing energy consumption. However, traditional working fluids used in these heat pumps generally contain a significant global warming potential (GWP), which might cause severe greenhouse effects if they are released. The goal of the emphasis on low-GWP (below 150) refrigerants is to further the vapor compression heat pumps. A classification system for vapor compression heat pumps is offered, with different boundaries based on the needed heat temperature and advancements in heat pump technology. A heat pump could be classified as a low temperature heat pump (LTHP), medium temperature heat pump (MTHP), high temperature heat pump (HTHP), or ultra-high temperature heat pump (UHTHP). The HTHP/UHTHP border is 160 °C, the MTHP/HTHP and LTHP/MTHP limits are 100 and 60 °C, respectively. The refrigerant is one of the most important parts of a vapor compression heat pump system. Presently, the main ways to choose a refrigerant are based on ozone depletion potential (ODP) and GWP, with GWP being the lowest possible value and ODP being zero. Pure low-GWP refrigerants, such as natural refrigerants (R718 and R744), hydrocarbons (R290, R600), hydrofluorocarbons (R152a and R161), hydrofluoroolefins (R1234yf, R1234ze(E)), and hydrochlorofluoroolefin (R1233zd(E)), were selected as candidates for vapor compression heat pump systems based on these selection principles. The performance, characteristics, and potential uses of these low-GWP refrigerants in heat pump systems are investigated in this paper. As vapor compression heat pumps with pure low-GWP refrigerants become more common, more and more low-grade heat can be recovered. This means that energy consumption would decrease. The research outputs showed that the refrigerants R718 for UHTHP application, R1233zd(E) for HTHP application, R600, R152a, R161, R1234ze(E) for MTHP, and R744, R290, and R1234yf for LTHP application are appropriate. The selection of an appropriate refrigerant should, in fact, take into consideration two different environmental and thermodynamic points of view. It might be argued that, depending on the situation, a trade-off between these two groups should constantly be considered. The environmental approach is now far stronger than it was previously, according to the European Union regulations. This will promote sustainable energy consumption and social development in addition to assisting in the reduction of greenhouse gas emissions and the management of global warming.

Keywords: vapor compression, global warming potential, heat pumps, greenhouse

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41 Biodegradation Ability of Polycyclic Aromatic Hydrocarbon (PAHs) Degrading Bacillus cereus Strain JMG-01 Isolated from PAHs Contaminated Soil

Authors: Momita Das, Sofia Banu, Jibon Kotoky

Abstract:

Environmental contamination of natural resources with persistent organic pollutants is of great world-wide apprehension. Polycyclic aromatic hydrocarbons (PAHs) are among the organic pollutants, released due to various anthropogenic activities. Due to their toxic, carcinogenic and mutagenic properties, PAHs are of environmental and human concern. Presently, bioremediation has evolved as the most promising biotechnology for cleanup of such contaminants because of its economical and less cost effectiveness. In the present study, distribution of 16 USEPA priority PAHs was determined in the soil samples collected from fifteen different sites of Guwahati City, the Gateway of the North East Region of India. The total concentrations of 16 PAHs (Σ16 PAHs) ranged from 42.7-742.3 µg/g. Higher concentration of total PAHs was found more in the Industrial areas compared to all the sites (742.3 µg/g and 628 µg/g). It is noted that among all the PAHs, Naphthalene, Acenaphthylene, Anthracene, Fluoranthene, Chrysene and Benzo(a)Pyrene were the most available and contain the higher concentration of all the PAHs. Since microbial activity has been deemed the most influential and significant cause of PAH removal; further, twenty-three bacteria were isolated from the most contaminated sites using the enrichment process. These strains were acclimatized to utilize naphthalene and anthracene, each at 100 µg/g concentration as sole carbon source. Among them, one Gram-positive strain (JMG-01) was selected, and biodegradation ability and initial catabolic genes of PAHs degradation were investigated. Based on 16S rDNA analysis, the isolate was identified as Bacillus cereus strain JMG-01. Topographic images obtained using Scanning Electron Microscope (SEM) and Atomic Force Microscope (AFM) at scheduled time intervals of 7, 14 and 21 days, determined the variation in cell morphology during the period of degradation. AFM and SEM micrograph of biomass showed high filamentous growth leading to aggregation of cells in the form of biofilm with reference to the incubation period. The percentage degradation analysis using gas chromatography and mass analyses (GC-MS) suggested that more than 95% of the PAHs degraded when the concentration was at 500 µg/g. Naphthalene, naphthalene-2-methy, benzaldehyde-4-propyl, 1, 2, benzene di-carboxylic acid and benzene acetic acid were the major metabolites produced after degradation. Moreover, PCR experiments with specific primers for catabolic genes, ndo B and Cat A suggested that JMG-01 possess genes for PAHs degradation. Thus, the study concludes that Bacillus cereus strain JMG-01 has efficient biodegrading ability and can trigger the clean-up of PAHs contaminated soil.

Keywords: AFM, Bacillus cereus strain JMG-01, degradation, polycyclic aromatic hydrocarbon, SEM

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