Search results for: polycyclic aromatic hydrocarbons (PAH)
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 577

Search results for: polycyclic aromatic hydrocarbons (PAH)

307 Physico-Chemical Properties of Silurian Hot Shale in Ahnet Basin, Algeria: Case Study Well ASS-1

Authors: Mohamed Mehdi Kadri

Abstract:

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

Procedia PDF Downloads 101
306 Graphene/ZnO/Polymer Nanocomposite Thin Film for Separation of Oil-Water Mixture

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

Procedia PDF Downloads 174
305 Geological Characteristics and Hydrocarbon Potential of M’Rar Formation Within NC-210, Atshan Saddle Ghadamis-Murzuq Basins, Libya

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

Procedia PDF Downloads 74
304 Modeling of Hydrogen Production by Inductively Coupled Methane Plasma for Input Power Pin=700W

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

Procedia PDF Downloads 165
303 Comparision of Bioleaching of Metals from Spent Petroleum Catalyst Using Acidithiobacillus Ferrooxidans and Acidthiobacillus Thiooxidans

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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302 Catalytic Pyrolysis of Sewage Sludge for Upgrading Bio-Oil Quality Using Sludge-Based Activated Char as an Alternative to HZSM5

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

Procedia PDF Downloads 179
301 Organic Matter Distribution in Bazhenov Source Rock: Insights from Sequential Extraction and Molecular Geochemistry

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

Procedia PDF Downloads 170
300 Functional Finishing of Organic Cotton Fabric Using Vetiver Root Extract

Authors: Sakeena Naikwadi, K. Jagaluraiah Sannapapamma

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Vetiveria zizanioides is an aromatic grass and traditionally been used in aromatherapy and ayurvedic medicine. Vetiver root is multi-functional biopolymer and has highly aromatic, antimicrobial, UV blocking, antioxidant properties suitable for textile finishing. The vetiver root (Gulabi) powder of different concentration (2, 4, 6,8 percent) were extracted by aqueous and solvent methods subjected to bioassay for antimicrobial efficiency and GCMS spectral analysis. The organic cotton fabric was finished with vetiver root extract (8 percent) by exhaust and pad dry cure methods. The finished fabric was assessed for functional properties viz., UV protective factor, antimicrobial efficiency and aroma intensity. The results revealed that Ethanol extraction showed a greater zone of inhibition compared to aqueous extract in root powder. Among the concentrations, 8 percent root extract in ethanol showed a greater zone of inhibition against gram-positive organism S. aureus and gram-negative organism E. coli. The major compounds present in vetiver root extracts were diethyl pathalate with greater percentage (87.73 %) followed by 7- Isopropyl dimethyl carboxylic acid (4.05 %), 2-butanone 4-trimethyle cyclohexen (1.21 %), phenanthrene carboxylic acid (1.03 %), naphthalene pentanoic acid (0.99 %), 1-phenanthrene carboxylic acid and 1 cyclohexenone 2-methyl oxobuty (0.89 %). The sample finished by pad dry cure method exhibited better UV protection even after 10th wash as compared to exhaust method. Vetiver extract treated samples exhibited maximum zone of inhibition against S. aureus than the E. coli organism. The vetiver root extract treated organic cotton fabric through pad dry cure method possessed good antimicrobial activity against S. aureus and E. coli even after 20th washes compared to vetiver root extract treated by exhaust method. The olfactory analysis was carried out by 30 panels of members and opined that vetiver root extract treated fabric has very good and pleasant aroma with better tactile properties that provide cooling, soothing effect and enhances the mood of the wearer. Vetiver root extract finished organic cotton fabric possessed aroma, antimicrobial and UV properties which are aptly suitable for medical and healthcare textiles viz., wound dressing, bandage gauze, surgical cloths, baby diapers and sanitary napkins. It can be used as after finishing agent for variegated garments and made-ups and can be replaced with commercial after finishing agents.

Keywords: antimicrobial, olfactory analysis, UV protection factor, vetiver root extract

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299 Effect of Natural Binder on Pang-Rum Hardness

Authors: Pattaranut Eakwaropas, Khemjira Jarmkom, Warachate Khobjai, Surachai Techaoei

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The aim of this study is to improve Pang-Rum (PR) hardness by adding natural binders. PR is one of Thai tradition aroma products. In the past, it was used for aesthetic propose on face and body with good odor. Nowadays, PR is not popular and going to be disappeared. Five natural materials, i.e. agar, rice flour, glutinous flour, corn starch, and tapioca starch were selected to use as binders. Binders were dissolved with boiled water into concentration 5% and 10% w/w except agar that was prepared 0.5% and 1% w/w. PR with and without binder were formulated. Physical properties, i.e. weight, shape, color, and hardness were evaluated. PR with 10% of corn starch solution had suitable hardness (14.2±0.9 kg) and the best appearance. In the future, it would be planned to study about odor and physical stability for decorated product development.

Keywords: aromatic water, hardness, natural binder, pang-rum

Procedia PDF Downloads 292
298 Industrial-Waste Management in Developing Countries: The Case of Algeria

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

Procedia PDF Downloads 338
297 Physico-Chemical and Biotechnological Characterization of Sheep’s Milk (Ovis aries) by Three Medicinal Plants Extracts

Authors: Fatima Bouazza, Khadija Khedid, Lamiae Amallah, Aziz Mouhaddach, Basma Boukour, Jihane Ennadir, Rachida Hassikou

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In order to combine milk and its derived products conservation and flavoring, Moroccans often used aromatic and medicinal plants. These plant extracts are endowed with several nutritive and therapeutic properties. This study constitutes a first national assessment of physico-chemical quality of sheep’s milk from moroccan Sardi breed and the evaluation of the antibacterial effect of three medicinal plants extracts: Aloe barbadensis Miller, Thymus satureioides and Mentha pulegium on flora isolated from this sheep's milk. 100 milk samples were collected in four regions of Morocco. The bacteria isolated were identified by classical and molecular methods (16S rRNA sequencing) and tested, according to the disk method, for their sensitivity to several antibiotics. The physico-chemical analyzes of sheep’s milk concerned the pH, titratable acidity, density, dry extract, freezing point and contents of: fat, proteins, lactose and calcium. The essential oils (EOs) of T. satureioides and M .pulegium were extracted by hydrodistillation and analyzed by GC / MS, while the Aloe vera leaf pulp was analyzed by the methods of Harborne and HPLC. A total number of 125 bacteria have been identified. Significant resistance to chemical antibiotics has been noted in LABs. The average temperature value of milk is around 57.15 °C, the pH is 6.56, the titratable acidity is around 3.4 ° D, the density is 1.035g / cm³ , the total dry extract is around 169.5g / l, the ash (9.8g / l), the freezing point (- 0.556 °C) while the average fat content is 67.85g / l . The samples richest in fat belong to the region of Settat, cradle of the Sardi breed, with a maximum average value of 74.4g / l. The average protein is 56g / l, lactose (39.92g / l), and calcium (1.855g / l). Analysis of the major components of EOs revealed the dominance of borneol in the case of T. satureioides and of pulegone in M. pulegium. Aloe vera gel contains alkaloids, flavonoids, catechic tannins, saponins and 1.60 µg / ml of aloin. The plant extracts have a bactericidal effect on E. coli, Klebsiellaoxytoca and Staphylococci and bacteriostatic effect on LABs of technological interest (Lactobacillus). As a result of this study, it is believed that the consumption of sardi sheep’s milk would be of nutritional benefit. Its richness in fat and proteins predisposes it for biotechnological development in the manufacture of cheese and yogurt. Also, the use of aromatic and medicinal plants, as natural additives would be of great benefit to flavor and maintain its quality.

Keywords: sheep’s milk, lactic flora, antimicrobial power, aloe barbadensis miller, thymus satureioides, mentha pulegium

Procedia PDF Downloads 126
296 Variation among East Wollega Coffee (Coffea arabica L.) Landraces for Quality Attributes

Authors: Getachew Weldemichael, Sentayehu Alamerew, Leta Tulu, Gezahegn Berecha

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Coffee quality improvement program is becoming the focus of coffee research, as the world coffee consumption pattern shifted to high-quality coffee. However, there is limited information on the genetic variation of C. Arabica for quality improvement in potential specialty coffee growing areas of Ethiopia. Therefore, this experiment was conducted with the objectives of determining the magnitude of variation among 105 coffee accessions collected from east Wollega coffee growing areas and assessing correlations between the different coffee qualities attributes. It was conducted in RCRD with three replications. Data on green bean physical characters (shape and make, bean color and odor) and organoleptic cup quality traits (aromatic intensity, aromatic quality, acidity, astringency, bitterness, body, flavor, and overall standard of the liquor) were recorded. Analysis of variance, clustering, genetic divergence, principal component and correlation analysis was performed using SAS software. The result revealed that there were highly significant differences (P<0.01) among the accessions for all quality attributes except for odor and bitterness. Among the tested accessions, EW104 /09, EW101 /09, EW58/09, EW77/09, EW35/09, EW71/09, EW68/09, EW96 /09, EW83/09 and EW72/09 had the highest total coffee quality values (the sum of bean physical and cup quality attributes). These genotypes could serve as a source of genes for green bean physical characters and cup quality improvement in Arabica coffee. Furthermore, cluster analysis grouped the coffee accessions into five clusters with significant inter-cluster distances implying that there is moderate diversity among the accessions and crossing accessions from these divergent inter-clusters would result in hetrosis and recombinants in segregating generations. The principal component analysis revealed that the first three principal components with eigenvalues greater than unity accounted for 83.1% of the total variability due to the variation of nine quality attributes considered for PC analysis, indicating that all quality attributes equally contribute to a grouping of the accessions in different clusters. Organoleptic cup quality attributes showed positive and significant correlations both at the genotypic and phenotypic levels, demonstrating the possibility of simultaneous improvement of the traits. Path coefficient analysis revealed that acidity, flavor, and body had a high positive direct effect on overall cup quality, implying that these traits can be used as indirect criteria to improve overall coffee quality. Therefore, it was concluded that there is considerable variation among the accessions, which need to be properly conserved for future improvement of the coffee quality. However, the variability observed for quality attributes must be further verified using biochemical and molecular analysis.

Keywords: accessions, Coffea arabica, cluster analysis, correlation, principal component

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295 Functionalization of Single-Walled Nanotubes by Synthesied Pigments

Authors: Shahab Zomorodbakhsh, Hayron Nesa Motevasel

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Water soluble compoundes were attached to single-walled carbon nanotubes (SWNTs) to form water-soluble nano pigments. functionalized SWNTs were then characterized by Fourier Transform Infrared spectroscopy (FT-IR), Raman spectroscopy, UV analysis, Transmission electron microscopy (TEM)and defunctionalization test and Representative results concerning the solubility. The product can be dissolved in water and High-resolution transmission electron microscope images showed that the SWNTs were efficiently functionalized, thus the p-stacking interaction between aromatic rings and COOH of SWNTs was considered responsible for the high solubility and High transmission electron in singlewall nanotubes.

Keywords: functionalized CNTs, singlewalled carbon nanotubes, water soluble compoundes, nano pigments

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294 Olefin and Paraffin Separation Using Simulations on Extractive Distillation

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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293 Liquid-Liquid Equilibrium Study in Solvent Extraction of o-Cresol from Coal Tar

Authors: Dewi Selvia Fardhyanti, Astrilia Damayanti

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Coal tar is a liquid by-product of the process of coal gasification and carbonation, also in some industries such as steel, power plant, cement, and others. This liquid oil mixture contains various kinds of useful compounds such as aromatic compounds and phenolic compounds. These compounds are widely used as raw material for insecticides, dyes, medicines, perfumes, coloring matters, and many others. This research investigates thermodynamic modelling of liquid-liquid equilibria (LLE) in solvent extraction of o-Cresol from the coal tar. The equilibria are modeled by ternary components of Wohl, Van Laar, and Three-Suffix Margules models. The values of the parameters involved are obtained by curve-fitting to the experimental data. Based on the comparison between calculated and experimental data, it turns out that among the three models studied, the Three-Suffix Margules seems to be the best to predict the LLE of o-Cresol for those system.

Keywords: coal tar, o-Cresol, Wohl, Van Laar, three-suffix margules

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292 Adsorption of Toluene from Aqueous Solutions by Porous Clay Hetero-Structures

Authors: F. Asadi, M. M. Zerafat, S. Sabbaghi

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Among water pollutants, volatile organic compounds can cause severe long lasting effects not only on biotic organism but also on human health. As a result, this material group has attracted more attention in recent years. Adsorption is one of the common processes for remediation of aromatic compounds. In this study, porous clay hetrostructers (PCHs) are synthesized through gallery template approach and cetyltrimethylammonium bromide and dodecylamine used as template and co-template, respectively. Porous clay is characterized by XRD and FTIR. Batch adsorption experiments were carried out to investigate the effect of various adsorption parameters like adsorbent dosage, pH, initial concentration and contact time. It was found that by increasing adsorbent dosage from 0.5gr/lit to 4gr/lit, toluene removal is increased from 34% to 88.1%. Increasing contact time and decreasing the pH of aqueous solution increases toluene removal efficiency.

Keywords: adsorption, clay, nano-porous, toluene

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291 Processes Controlling Release of Phosphorus (P) from Catchment Soils and the Relationship between Total Phosphorus (TP) and Humic Substances (HS) in Scottish Loch Waters

Authors: Xiaoyun Hui, Fiona Gentle, Clemens Engelke, Margaret C. Graham

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Although past work has shown that phosphorus (P), an important nutrient, may form complexes with aqueous humic substances (HS), the principal component of natural organic matter, the nature of such interactions is poorly understood. Humic complexation may not only enhance P concentrations but it may change its bioavailability within such waters and, in addition, influence its transport within catchment settings. This project is examining the relationships and associations of P, HS, and iron (Fe) in Loch Meadie, Sutherland, North Scotland, a mesohumic freshwater loch which has been assessed as reference condition with respect to P. The aim is to identify characteristic spectroscopic parameters which can enhance the performance of the model currently used to predict reference condition TP levels for highly-coloured Scottish lochs under the Water Framework Directive. In addition to Loch Meadie, samples from other reference condition lochs in north Scotland and Shetland were analysed. By including different types of reference condition lochs (clear water, mesohumic and polyhumic water) this allowed the relationship between total phosphorus (TP) and HS to be more fully explored. The pH, [TP], [Fe], UV/Vis absorbance/spectra, [TOC] and [DOC] for loch water samples have been obtained using accredited methods. Loch waters were neutral to slightly acidic/alkaline (pH 6-8). [TP] in loch waters were lower than 50 µg L-1, and in Loch Meadie waters were typically <10 µg L-1. [Fe] in loch waters were mainly <0.6 mg L-1, but for some loch water samples, [Fe] were in the range 1.0-1.8 mg L-1and there was a positive correlation with [TOC] (r2=0.61). Lochs were classified as clear water, mesohumic or polyhumic based on water colour. The range of colour values of sampled lochs in each category were 0.2–0.3, 0.2–0.5 and 0.5–0.8 a.u. (10 mm pathlength), respectively. There was also a strong positive correlation between [DOC] and water colour (R2=0.84). The UV/Vis spectra (200-700 nm) for water samples were featureless with only a slight “shoulder” observed in the 270–290 nm region. Ultrafiltration was then used to separate colloidal and truly dissolved components from the loch waters and, since it contained the majority of aqueous P and Fe, the colloidal component was fractionated by gel filtration chromatography method. Gel filtration chromatographic fractionation of the colloids revealed two brown-coloured bands which had distinctive UV/Vis spectral features. The first eluting band had larger and more aromatic HS molecules than the second band, and in addition both P and Fe were primarily associated with the larger, more aromatic HS. This result demonstrated that P was able to form complexes with Fe-rich components of HS, and thus provided a scientific basis for the significant correlation between [Fe] and [TP] that the previous monitoring data of reference condition lochs from Scottish Environment Protection Agency (SEPA) showed. The distinctive features of the HS will be used as the basis for an improved spectroscopic tool.

Keywords: total phosphorus, humic substances, Scottish loch water, WFD model

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290 Determination of Physical Properties of Crude Oil Distillates by Near-Infrared Spectroscopy and Multivariate Calibration

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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289 Treatment of Onshore Petroleum Drill Cuttings via Soil Washing Process: Characterization and Optimal Conditions

Authors: T. Poyai, P. Painmanakul, N. Chawaloesphonsiya, P. Dhanasin, C. Getwech, P. Wattana

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Drilling is a key activity in oil and gas exploration and production. Drilling always requires the use of drilling mud for lubricating the drill bit and controlling the subsurface pressure. As drilling proceeds, a considerable amount of cuttings or rock fragments is generated. In general, water or Water Based Mud (WBM) serves as drilling fluid for the top hole section. The cuttings generated from this section is non-hazardous and normally applied as fill materials. On the other hand, drilling the bottom hole to reservoir section uses Synthetic Based Mud (SBM) of which synthetic oils are composed. The bottom-hole cuttings, SBM cuttings, is regarded as a hazardous waste, in accordance with the government regulations, due to the presence of hydrocarbons. Currently, the SBM cuttings are disposed of as an alternative fuel and raw material in cement kiln. Instead of burning, this work aims to propose an alternative for drill cuttings management under two ultimate goals: (1) reduction of hazardous waste volume; and (2) making use of the cleaned cuttings. Soil washing was selected as the major treatment process. The physiochemical properties of drill cuttings were analyzed, such as size fraction, pH, moisture content, and hydrocarbons. The particle size of cuttings was analyzed via light scattering method. Oil present in cuttings was quantified in terms of total petroleum hydrocarbon (TPH) through gas chromatography equipped with flame ionization detector (GC-FID). Other components were measured by the standard methods for soil analysis. Effects of different washing agents, liquid-to-solid (L/S) ratio, washing time, mixing speed, rinse-to-solid (R/S) ratio, and rinsing time were also evaluated. It was found that drill cuttings held the electrical conductivity of 3.84 dS/m, pH of 9.1, and moisture content of 7.5%. The TPH in cuttings existed in the diesel range with the concentration ranging from 20,000 to 30,000 mg/kg dry cuttings. A majority of cuttings particles held a mean diameter of 50 µm, which represented silt fraction. The results also suggested that a green solvent was considered most promising for cuttings treatment regarding occupational health, safety, and environmental benefits. The optimal washing conditions were obtained at L/S of 5, washing time of 15 min, mixing speed of 60 rpm, R/S of 10, and rinsing time of 1 min. After washing process, three fractions including clean cuttings, spent solvent, and wastewater were considered and provided with recommendations. The residual TPH less than 5,000 mg/kg was detected in clean cuttings. The treated cuttings can be then used for various purposes. The spent solvent held the calorific value of higher than 3,000 cal/g, which can be used as an alternative fuel. Otherwise, the recovery of the used solvent can be conducted using distillation or chromatography techniques. Finally, the generated wastewater can be combined with the produced water and simultaneously managed by re-injection into the reservoir.

Keywords: drill cuttings, green solvent, soil washing, total petroleum hydrocarbon (TPH)

Procedia PDF Downloads 155
288 Inhibition of Mild Steel Corrosion in Hydrochloric Acid Medium Using an Aromatic Hydrazide Derivative

Authors: Preethi Kumari P., Shetty Prakasha, Rao Suma A.

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Mild steel has been widely employed as construction materials for pipe work in the oil and gas production such as down hole tubular, flow lines and transmission pipelines, in chemical and allied industries for handling acids, alkalis and salt solutions due to its excellent mechanical property and low cost. Acid solutions are widely used for removal of undesirable scale and rust in many industrial processes. Among the commercially available acids hydrochloric acid is widely used for pickling, cleaning, de-scaling and acidization of oil process. Mild steel exhibits poor corrosion resistance in presence of hydrochloric acid. The high reactivity of mild steel in presence of hydrochloric acid is due to the soluble nature of ferrous chloride formed and the cementite phase (Fe3C) normally present in the steel is also readily soluble in hydrochloric acid. Pitting attack is also reported to be a major form of corrosion in mild steel in the presence of high concentrations of acids and thereby causing the complete destruction of metal. Hydrogen from acid reacts with the metal surface and makes it brittle and causes cracks, which leads to pitting type of corrosion. The use of chemical inhibitor to minimize the rate of corrosion has been considered to be the first line of defense against corrosion. In spite of long history of corrosion inhibition, a highly efficient and durable inhibitor that can completely protect mild steel in aggressive environment is yet to be realized. It is clear from the literature review that there is ample scope for the development of new organic inhibitors, which can be conveniently synthesized from relatively cheap raw materials and provide good inhibition efficiency with least risk of environmental pollution. The aim of the present work is to evaluate the electrochemical parameters for the corrosion inhibition behavior of an aromatic hydrazide derivative, 4-hydroxy- N '-[(E)-1H-indole-2-ylmethylidene)] benzohydrazide (HIBH) on mild steel in 2M hydrochloric acid using Tafel polarization and electrochemical impedance spectroscopy (EIS) techniques at 30-60 °C. The results showed that inhibition efficiency increased with increase in inhibitor concentration and decreased marginally with increase in temperature. HIBH showed a maximum inhibition efficiency of 95 % at 8×10-4 M concentration at 30 °C. Polarization curves showed that HIBH act as a mixed-type inhibitor. The adsorption of HIBH on mild steel surface obeys the Langmuir adsorption isotherm. The adsorption process of HIBH at the mild steel/hydrochloric acid solution interface followed mixed adsorption with predominantly physisorption at lower temperature and chemisorption at higher temperature. Thermodynamic parameters for the adsorption process and kinetic parameters for the metal dissolution reaction were determined.

Keywords: electrochemical parameters, EIS, mild steel, tafel polarization

Procedia PDF Downloads 337
287 Process Simulation of 1-Butene Separation from C4 Mixture by Extractive Distillation

Authors: Muhammad Naeem, Abdulrahman A. Al-Rabiah, Wasif Mughees

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Technical mixture of C4 containing 1-butene and n-butane are very close to each other with regard 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 plays 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 number of proposed plates were 30, which shows that the separation process can be economized.

Keywords: extractive distillation, 1-butene, aspen plus, ACN solvent

Procedia PDF Downloads 547
286 Thermodynamic Modelling of Liquid-Liquid Equilibria (LLE) in the Separation of p-Cresol from the Coal Tar by Solvent Extraction

Authors: D. S. Fardhyanti, Megawati, W. B. Sediawan

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Coal tar is a liquid by-product of the process of coal gasification and carbonation. This liquid oil mixture contains various kinds of useful compounds such as aromatic compounds and phenolic compounds. These compounds are widely used as raw material for insecticides, dyes, medicines, perfumes, coloring matters, and many others. This research investigates thermodynamic modelling of liquid-liquid equilibria (LLE) in the separation of phenol from the coal tar by solvent extraction. The equilibria are modeled by ternary components of Wohl, Van Laar, and Three-Suffix Margules models. The values of the parameters involved are obtained by curve-fitting to the experimental data. Based on the comparison between calculated and experimental data, it turns out that among the three models studied, the Three-Suffix Margules seems to be the best to predict the LLE of p-Cresol mixtures for those system.

Keywords: coal tar, phenol, Wohl, Van Laar, Three-Suffix Margules

Procedia PDF Downloads 259
285 Synthesis, Characterization and Catalytic Applications of Divalent Schiff Base Metal Complexes Derived from Amino Coumarins and Substituted Benzaldehydes and Acetophenones

Authors: Srinivas Nerella

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A series of new heterodentate N, O-donor ligands derived from condensing 3-amino Coumarins with hydroxy benzaldehydes and acetophenones were used to afford new mononuclear Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) coordination compounds. All the complexes were characterized by IR, 1H-NMR, 13C-NMR, Mass, ESR, Electronic spectra, Conductance, Magnetic and Thermal studies. The ligands show hexa coordination in Mn(II), Co(II), Ni(II), and Pd(II) complexes resulting octahedral geometries, while the ligands in Zn(II) and Cu(II) complexes show tetra coordination resulting tetrahedral and square planar geometries respectively. These mononuclear complexes were investigated as catalysts in the hydrothiolation of aromatic and aliphatic alkynes with thiols. These metal complexes were acted as versatile catalysts and gave good yields.

Keywords: schiff bases, divalent metal complexes of schiff bases, Catalytic activity, hydrothiolation

Procedia PDF Downloads 416
284 Application of Waterflooding to the Kashkari Oil Field in Northern Afghanistan

Authors: Zabihullah Mahdi, Mahdi Nayab, Sadaf Jalal, Navid Seddiqi

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Hydrocarbons represent an important natural resource for the rehabilitation and sustainable development of Afghanistan. In this paper, the use of waterflooding is demonstrated for the petroleum reservoirs of the Kashkari oil field in northern Afghanistan. The technique is based on the Buckley–Leverett frontal-displacement theory, which enables computation of the progress of the waterfront in the reservoir. The relative permeabilities of oil and water, the residual oil saturation, and the irreducible water saturation are obtained from a laboratory experiment. The technique is applied to the laboratory plane-reservoir model to investigate the displacement mechanism and is then compared with the theoretical calculation. Lastly, the technique is applied to the Kashkari oil field to predict the feasible amount of oil that could be produced from this reservoir.

Keywords: Buckley–Leverett, waterflooding, petroleum reservoir engineering, two-phase flow, immiscible displacement, porous media, relative permeability

Procedia PDF Downloads 205
283 Solar Photocatalytic Degradation of Phenol in Aqueous Solutions Using Titanium Dioxide

Authors: Mohamed Gar Alalm, Ahmed Tawfik

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In this study, photo-catalytic degradation of phenol by titanium dioxide (TiO2) in aqueous solution was evaluated. The UV energy of solar light was utilized by compound parabolic collectors (CPCs) technology. The effect of irradiation time, initial pH, and dosage of TiO2 were investigated. Aromatic intermediates (catechol, benzoquinone, and hydroquinone) were quantified during the reaction to study the pathways of the oxidation process. 94.5% degradation efficiency of phenol was achieved after 150 minutes of irradiation when the initial concentration was 100 mg/L. The dosage of TiO2 significantly affected the degradation efficiency of phenol. The observed optimum pH for the reaction was 5.2. Phenol photo-catalytic degradation fitted to the pseudo-first order kinetic according to Langmuir–Hinshelwood model.

Keywords: compound parabolic collectors, phenol, photo-catalytic, titanium dioxide

Procedia PDF Downloads 409
282 Using Inverted 4-D Seismic and Well Data to Characterise Reservoirs from Central Swamp Oil Field, Niger Delta

Authors: Emmanuel O. Ezim, Idowu A. Olayinka, Michael Oladunjoye, Izuchukwu I. Obiadi

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Monitoring of reservoir properties prior to well placements and production is a requirement for optimisation and efficient oil and gas production. This is usually done using well log analyses and 3-D seismic, which are often prone to errors. However, 4-D (Time-lapse) seismic, incorporating numerous 3-D seismic surveys of the same field with the same acquisition parameters, which portrays the transient changes in the reservoir due to production effects over time, could be utilised because it generates better resolution. There is, however dearth of information on the applicability of this approach in the Niger Delta. This study was therefore designed to apply 4-D seismic, well-log and geologic data in monitoring of reservoirs in the EK field of the Niger Delta. It aimed at locating bypassed accumulations and ensuring effective reservoir management. The Field (EK) covers an area of about 1200km2 belonging to the early (18ma) Miocene. Data covering two 4-D vintages acquired over a fifteen-year interval were obtained from oil companies operating in the field. The data were analysed to determine the seismic structures, horizons, Well-to-Seismic Tie (WST), and wavelets. Well, logs and production history data from fifteen selected wells were also collected from the Oil companies. Formation evaluation, petrophysical analysis and inversion alongside geological data were undertaken using Petrel, Shell-nDi, Techlog and Jason Software. Well-to-seismic tie, formation evaluation and saturation monitoring using petrophysical and geological data and software were used to find bypassed hydrocarbon prospects. The seismic vintages were interpreted, and the amounts of change in the reservoir were defined by the differences in Acoustic Impedance (AI) inversions of the base and the monitor seismic. AI rock properties were estimated from all the seismic amplitudes using controlled sparse-spike inversion. The estimated rock properties were used to produce AI maps. The structural analysis showed the dominance of NW-SE trending rollover collapsed-crest anticlines in EK with hydrocarbons trapped northwards. There were good ties in wells EK 27, 39. Analysed wavelets revealed consistent amplitude and phase for the WST; hence, a good match between the inverted impedance and the good data. Evidence of large pay thickness, ranging from 2875ms (11420 TVDSS-ft) to about 2965ms, were found around EK 39 well with good yield properties. The comparison between the base of the AI and the current monitor and the generated AI maps revealed zones of untapped hydrocarbons as well as assisted in determining fluids movement. The inverted sections through EK 27, 39 (within 3101 m - 3695 m), indicated depletion in the reservoirs. The extent of the present non-uniform gas-oil contact and oil-water contact movements were from 3554 to 3575 m. The 4-D seismic approach led to better reservoir characterization, well development and the location of deeper and bypassed hydrocarbon reservoirs.

Keywords: reservoir monitoring, 4-D seismic, well placements, petrophysical analysis, Niger delta basin

Procedia PDF Downloads 117
281 Synthesis of Highly Valuable Fuel Fractions from Waste Date Seeds Oil

Authors: Farrukh Jamil, Ala'A H. Al-Muhtaseb, Lamya Al-Haj, Mohab A. Al-Hinai

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Environmental problems and the security of energy supply have motivated the attention in the expansion of alternatives for fossil based fuels. Biomass has been recognized as a capable resource because it is plentifully available and in principle carbon dioxide neutral. Present study focuses on utilization date seeds oil for synthesizing high value fuels formulations such as green diesel and jet fuel. The hydrodeoxygenation of date seeds oil occurred to be highly efficient at following operating conditions temperature 300°C pressure 10bar with continuous stirring at 500 rpm. Products characterization revealed the efficiency of hydrodeoxygenation by formation of linear hydrocarbons (paraffin) in larger fraction. Based on the type of components in product oil it was calculated that maximum fraction lies within the range of green diesel 72.78 % then jet fuel 28.25 % by using Pt/C catalyst. It can be concluded that waste date seeds oil has potential to be used for obtaining high value products.

Keywords: date seeds, hydrodeoxygenation, paraffin, deoxygenation

Procedia PDF Downloads 266
280 Interfacial Reactions between Aromatic Polyamide Fibers and Epoxy Matrix

Authors: Khodzhaberdi Allaberdiev

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In order to understand the interactions on the interface polyamide fibers and epoxy matrix in fiber- reinforced composites were investigated industrial aramid fibers: armos, svm, terlon using individual epoxy matrix components, epoxies: diglycidyl ether of bisphenol A (DGEBA), three- and diglycidyl derivatives of m, p-amino-, m, p-oxy-, o, m,p-carboxybenzoic acids, the models: curing agent, aniline and the compound, that depict of the structure the primary addition reaction the amine to the epoxy resin, N-di (oxyethylphenoxy) aniline. The chemical structure of the surface of untreated and treated polyamide fibers analyzed using Fourier transform infrared spectroscopy (FTIR). The impregnation of fibers with epoxy matrix components and N-di (oxyethylphenoxy) aniline has been carried out by heating 150˚C (6h). The optimum fiber loading is at 65%.The result a thermal treatment is the covalent bonds formation , derived from a combined of homopolymerization and crosslinking mechanisms in the interfacial region between the epoxy resin and the surface of fibers. The reactivity of epoxy resins on interface in microcomposites (MC) also depends from processing aids treated on surface of fiber and the absorbance moisture. The influences these factors as evidenced by the conversion of epoxy groups values in impregnated with DGEBA of the terlons: industrial, dried (in vacuum) and purified samples: 5.20 %, 4.65% and 14.10%, respectively. The same tendency for svm and armos fibers is observed. The changes in surface composition of these MC were monitored by X-ray photoelectron spectroscopy (XPS). In the case of the purified fibers, functional groups of fibers act as well as a catalyst and curing agent of epoxy resin. It is found that the value of the epoxy groups conversion for reinforced formulations depends on aromatic polyamides nature and decreases in the order: armos >svm> terlon. This difference is due of the structural characteristics of fibers. The interfacial interactions also examined between polyglycidyl esters substituted benzoic acids and polyamide fibers in the MC. It is found that on interfacial interactions these systems influences as well as the structure and the isomerism of epoxides. The IR-spectrum impregnated fibers with aniline showed that the polyamide fibers appreciably with aniline do not react. FTIR results of treated fibers with N-di (oxyethylphenoxy) aniline fibers revealed dramatically changes IR-characteristic of the OH groups of the amino alcohol. These observations indicated hydrogen bondings and covalent interactions between amino alcohol and functional groups of fibers. This result also confirms appearance of the exo peak on Differential Scanning Calorimetry (DSC) curve of the MC. Finally, the theoretical evaluation non-covalent interactions between individual epoxy matrix components and fibers has been performed using the benzanilide and its derivative contaning the benzimidazole moiety as a models of terlon and svm,armos, respectively. Quantum-topological analysis also demonstrated the existence hydrogen bond between amide group of models and epoxy matrix components.All the results indicated that on the interface polyamide fibers and epoxy matrix exist not only covalent, but and non-covalent the interactions during the preparation of MC.

Keywords: epoxies, interface, modeling, polyamide fibers

Procedia PDF Downloads 267
279 Highly Selective Phosgene Free Synthesis of Methylphenylcarbamate from Aniline and Dimethyl Carbonate over Heterogeneous Catalyst

Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

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Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

Procedia PDF Downloads 276
278 Influence of Silica Surface Hydrophilicity on Adsorbed Water and Isopropanol Studied by in-situ NMR

Authors: Hyung T. Kwak, Jun Gao, Yao An, Alfred Kleinhammes, Yue Wu

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Surface wettability is a crucial factor in oil recovery. In oil industry, the rock wettability involves the interplay between water, oil, and solid surface. Therefore, studying the interplay between adsorptions of water and hydrocarbon molecules on solid surface would be very informative for understanding rock wettability. Here we use the in-situ Nuclear Magnetic Resonance (NMR) gas isotherm technique to study competitive adsorptions of water and isopropanol, an intermediate step from hydrocarbons. This in-situ NMR technique obtains information on thermodynamic properties such as the isotherm, molecular dynamics via spin relaxation measurements, and adsorption kinetics such as how fast the system can reach thermal equilibrium after changes of vapor pressures. Using surfaces of silica glass beads, which can be modified from hydrophilic to hydrophobic, we obtained information on the influence of surface hydrophilicity on the state of surface water via obtained thermodynamic and dynamic properties.

Keywords: Wettability, NMR, Gas Isotherm, Hydrophilicity, adsorption

Procedia PDF Downloads 179