Search results for: bubble column reactor
Commenced in January 2007
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Paper Count: 1532

Search results for: bubble column reactor

62 Phenolic Composition and Contribution of Individual Compounds to Antioxidant Activity of Malus domestica Borkh Fruit Cultivars

Authors: Raudone Lina, Raudonis Raimondas, Liaudanskas Mindaugas, Pukalskas Audrius, Viskelis Pranas, Janulis Valdimaras

Abstract:

Human health fortification, its protection and disease prophylaxis are the main problems of the health care systems. Plant origin materials and their preparations are applied for the prevention of the common diseases. Oxidative stress takes part in the pathogenesis of many autoimmune, neurodegenerative, tumor and ageing processes. The antioxidants are able to protect the human body from the free radicals and to stop the progression of numerous chronic diseases. The research of plant origin materials is relevant for the search of natural antioxidants. A group of compounds that gained scientific attention due to antioxidant properties and effects on human health are phenolic compounds. Phenolic compounds are widely abundant in various parts of plants, i.e. leaves, stems, roots, flowers and fruits. Most commonly consumed fruits all over the world are apples. It is very important to analyze the antioxidant activity of apples as they are extensively used in the prevention of various diseases. The aim of this study was to determine the antioxidant profiles of Malus domestica Borkh fruit cultivars (Aldas, Auksis, Connel Red, Ligol, Lodel, Rajka) and to identify the phenolic compounds with potent contribution to antioxidant activity. Nineteen constituents were identified in apple cultivars using ultra high performance liquid chromatography coupled to quadruple and time-of-flight mass spectrometers (UPLC–QTOF–MS). Phytochemical profile was constituted of phenolic acids, procyanidins, quercetin derivatives and dihydrochalcones. Reducing and radical scavenging activities of individual constituents were determined using high performance liquid chromatography (HPLC) coupled to post-column FRAP and ABTS assay, respectively. Significant differences of total radical scavenging and reducing activity (expressed as trolox equivalents, TE µmol/g) were determined between the investigated cultivars. Chlorogenic acid and complex of procyanidins were the main contributors to antioxidant activity determining up to 35 % and 55 % of total TE values, respectively. Determined phenolic composition and antioxidant activity significantly depend on apple cultivars. It is important to determine the individual compounds that are significant for antioxidant activity and that could be investigated in vivo systems. The identification of the antioxidants provides information for the further research of standardized extracts that could be used for pharmaceutical preparations with specific phenolic traits.

Keywords: FRAP, ABTS, antioxidant, phenolic, apples, chlorogenic acid

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61 Leuco Dye-Based Thermochromic Systems for Application in Temperature Sensing

Authors: Magdalena Wilk-Kozubek, Magdalena Rowińska, Krzysztof Rola, Joanna Cybińska

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Leuco dye-based thermochromic systems are classified as intelligent materials because they exhibit thermally induced color changes. Thanks to this feature, they are mainly used as temperature sensors in many industrial sectors. For example, placing a thermochromic material on a chemical reactor may warn about exceeding the maximum permitted temperature for a chemical process. Usually two components, a color former and a developer are needed to produce a system with irreversible color change. The color former is an electron donating (proton accepting) compound such as fluoran leuco dye. The developer is an electron accepting (proton donating) compound such as organic carboxylic acid. When the developer melts, the color former - developer complex is created and the termochromic system becomes colored. Typically, the melting point of the applied developer determines the temperature at which the color change occurs. When the lactone ring of the color former is closed, then the dye is in its colorless state. The ring opening, induced by the addition of a proton, causes the dye to turn into its colored state. Since the color former and the developer are often solid, they can be incorporated into polymer films to facilitate their practical use in industry. The objective of this research was to fabricate a leuco dye-based termochromic system that will irreversibly change color after reaching the temperature of 100°C. For this purpose, benzofluoran leuco dye (as color former) and phenoxyacetic acid (as developer with a melting point of 100°C) were introduced into the polymer films during the drop casting process. The film preparation process was optimized in order to obtain thin films with appropriate properties such as transparency, flexibility and homogeneity. Among the optimized factors were the concentration of benzofluoran leuco dye and phenoxyacetic acid, the type, average molecular weight and concentration of the polymer, and the type and concentration of the surfactant. The selected films, containing benzofluoran leuco dye and phenoxyacetic acid, were combined by mild heat treatment. Structural characterization of single and combined films was carried out by FTIR spectroscopy, morphological analysis was performed by optical microscopy and SEM, phase transitions were examined by DSC, color changes were investigated by digital photography and UV-Vis spectroscopy, while emission changes were studied by photoluminescence spectroscopy. The resulting thermochromic system is colorless at room temperature, but after reaching 100°C the developer melts and it turns irreversibly pink. Therefore, it could be used as an additional sensor to warn against boiling of water in power plants using water cooling. Currently used electronic temperature indicators are prone to faults and unwanted third-party actions. The sensor constructed in this work is transparent, thanks to which it can be unnoticed by an outsider and constitute a reliable reference for the person responsible for the apparatus.

Keywords: color developer, leuco dye, thin film, thermochromism

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60 Finite Element Analysis of the Anaconda Device: Efficiently Predicting the Location and Shape of a Deployed Stent

Authors: Faidon Kyriakou, William Dempster, David Nash

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Abdominal Aortic Aneurysm (AAA) is a major life-threatening pathology for which modern approaches reduce the need for open surgery through the use of stenting. The success of stenting though is sometimes jeopardized by the final position of the stent graft inside the human artery which may result in migration, endoleaks or blood flow occlusion. Herein, a finite element (FE) model of the commercial medical device AnacondaTM (Vascutek, Terumo) has been developed and validated in order to create a numerical tool able to provide useful clinical insight before the surgical procedure takes place. The AnacondaTM device consists of a series of NiTi rings sewn onto woven polyester fabric, a structure that despite its column stiffness is flexible enough to be used in very tortuous geometries. For the purposes of this study, a FE model of the device was built in Abaqus® (version 6.13-2) with the combination of beam, shell and surface elements; the choice of these building blocks was made to keep the computational cost to a minimum. The validation of the numerical model was performed by comparing the deployed position of a full stent graft device inside a constructed AAA with a duplicate set-up in Abaqus®. Specifically, an AAA geometry was built in CAD software and included regions of both high and low tortuosity. Subsequently, the CAD model was 3D printed into a transparent aneurysm, and a stent was deployed in the lab following the steps of the clinical procedure. Images on the frontal and sagittal planes of the experiment allowed the comparison with the results of the numerical model. By overlapping the experimental and computational images, the mean and maximum distances between the rings of the two models were measured in the longitudinal, and the transverse direction and, a 5mm upper bound was set as a limit commonly used by clinicians when working with simulations. The two models showed very good agreement of their spatial positioning, especially in the less tortuous regions. As a result, and despite the inherent uncertainties of a surgical procedure, the FE model allows confidence that the final position of the stent graft, when deployed in vivo, can also be predicted with significant accuracy. Moreover, the numerical model run in just a few hours, an encouraging result for applications in the clinical routine. In conclusion, the efficient modelling of a complicated structure which combines thin scaffolding and fabric has been demonstrated to be feasible. Furthermore, the prediction capabilities of the location of each stent ring, as well as the global shape of the graft, has been shown. This can allow surgeons to better plan their procedures and medical device manufacturers to optimize their designs. The current model can further be used as a starting point for patient specific CFD analysis.

Keywords: AAA, efficiency, finite element analysis, stent deployment

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59 Enhancing of Antibacterial Activity of Essential Oil by Rotating Magnetic Field

Authors: Tomasz Borowski, Dawid Sołoducha, Agata Markowska-Szczupak, Aneta Wesołowska, Marian Kordas, Rafał Rakoczy

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Essential oils (EOs) are fragrant volatile oils obtained from plants. These are used for cooking (for flavor and aroma), cleaning, beauty (e.g., rosemary essential oil is used to promote hair growth), health (e.g. thyme essential oil cures arthritis, normalizes blood pressure, reduces stress on the heart, cures chest infection and cough) and in the food industry as preservatives and antioxidants. Rosemary and thyme essential oils are considered the most eminent herbs based on their history and medicinal properties. They possess a wide range of activity against different types of bacteria and fungi compared with the other oils in both in vitro and in vivo studies. However, traditional uses of EOs are limited due to rosemary and thyme oils in high concentrations can be toxic. In light of the accessible data, the following hypothesis was put forward: Low frequency rotating magnetic field (RMF) increases the antimicrobial potential of EOs. The aim of this work was to investigate the antimicrobial activity of commercial Salvia Rosmarinus L. and Thymus vulgaris L. essential oil from Polish company Avicenna-Oil under Rotating Magnetic Field (RMF) at f = 25 Hz. The self-constructed reactor (MAP) was applied for this study. The chemical composition of oils was determined by gas chromatography coupled with mass spectrometry (GC-MS). Model bacteria Escherichia coli K12 (ATCC 25922) was used. Minimum inhibitory concentrations (MIC) against E. coli were determined for the essential oils. Tested oils in very small concentrations were prepared (from 1 to 3 drops of essential oils per 3 mL working suspensions). From the results of disc diffusion assay and MIC tests, it can be concluded that thyme oil had the highest antibacterial activity against E. coli. Moreover, the study indicates the exposition to the RMF, as compared to the unexposed controls causing an increase in the efficacy of antibacterial properties of tested oils. The extended radiation exposure to RMF at the frequency f= 25 Hz beyond 160 minutes resulted in a significant increase in antibacterial potential against E. coli. Bacteria were killed within 40 minutes in thyme oil in lower tested concentration (1 drop of essential oils per 3 mL working suspension). Rapid decrease (>3 log) of bacteria number was observed with rosemary oil within 100 minutes (in concentration 3 drops of essential oils per 3 mL working suspension). Thus, a method for improving the antimicrobial performance of essential oil in low concentrations was developed. However, it still remains to be investigated how bacteria get killed by the EOs treated by an electromagnetic field. The possible mechanisms relies on alteration in the permeability of ionic channels in ionic channels in the bacterial cell walls that transport in the cells was proposed. For further studies, it is proposed to examine other types of essential oils and other antibiotic-resistant bacteria (ARB), which are causing a serious concern throughout the world.

Keywords: rotating magnetic field, rosemary, thyme, essential oils, Escherichia coli

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58 Catalytic Ammonia Decomposition: Cobalt-Molybdenum Molar Ratio Effect on Hydrogen Production

Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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57 Nonconventional Method for Separation of Rosmarinic Acid: Synergic Extraction

Authors: Lenuta Kloetzer, Alexandra C. Blaga, Dan Cascaval, Alexandra Tucaliuc, Anca I. Galaction

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Rosmarinic acid, an ester of caffeic acid and 3-(3,4-dihydroxyphenyl) lactic acid, is considered a valuable compound for the pharmaceutical and cosmetic industries due to its antimicrobial, antioxidant, antiviral, anti-allergic, and anti-inflammatory effects. It can be obtained by extraction from vegetable or animal materials, by chemical synthesis and biosynthesis. Indifferent of the method used for rosmarinic acid production, the separation and purification process implies high amount of raw materials and laborious stages leading to high cost for and limitations of the separation technology. This study focused on separation of rosmarinic acid by synergic reactive extraction with a mixture of two extractants, one acidic (acid di-(2ethylhexyl) phosphoric acid, D2EHPA) and one with basic character (Amberlite LA-2). The studies were performed in experimental equipment consisting of an extraction column where the phases’ mixing was made by mean of a perforated disk with 45 mm diameter and 20% free section, maintained at the initial contact interface between the aqueous and organic phases. The vibrations had a frequency of 50 s⁻¹ and 5 mm amplitude. The extraction was carried out in two solvents with different dielectric constants (n-heptane and dichloromethane) in which the extractants mixture of varying concentration was dissolved. The pH-value of initial aqueous solution was varied between 1 and 7. The efficiency of the studied extraction systems was quantified by distribution and synergic coefficients. For calculating these parameters, the rosmarinic acid concentration in the initial aqueous solution and in the raffinate have been measured by HPLC. The influences of extractants concentrations and solvent polarity on the efficiency of rosmarinic acid separation by synergic extraction with a mixture of Amberlite LA-2 and D2EHPA have been analyzed. In the reactive extraction system with a constant concentration of Amberlite LA-2 in the organic phase, the increase of D2EHPA concentration leads to decrease of the synergic coefficient. This is because the increase of D2EHPA concentration prevents the formation of amine adducts and, consequently, affects the hydrophobicity of the interfacial complex with rosmarinic acid. For these reasons, the diminution of synergic coefficient is more important for dichloromethane. By maintaining a constant value of D2EHPA concentration and increasing the concentration of Amberlite LA-2, the synergic coefficient could become higher than 1, its highest values being reached for n-heptane. Depending on the solvent polarity and D2EHPA amount in the solvent phase, the synergic effect is observed for Amberlite LA-2 concentrations over 20 g/l dissolved in n-heptane. Thus, by increasing the concentration of D2EHPA from 5 to 40 g/l, the minimum concentration value of Amberlite LA-2 corresponding to synergism increases from 20 to 40 g/l for the solvent with lower polarity, namely, n-heptane, while there is no synergic effect recorded for dichloromethane. By analysing the influences of the main factors (organic phase polarity, extractant concentration in the mixture) on the efficiency of synergic extraction of rosmarinic acid, the most important synergic effect was found to correspond to the extractants mixture containing 5 g/l D2EHPA and 40 g/l Amberlite LA-2 dissolved in n-heptane.

Keywords: Amberlite LA-2, di(2-ethylhexyl) phosphoric acid, rosmarinic acid, synergic effect

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56 Traumatic Brain Injury Induced Lipid Profiling of Lipids in Mice Serum Using UHPLC-Q-TOF-MS

Authors: Seema Dhariwal, Kiran Maan, Ruchi Baghel, Apoorva Sharma, Poonam Rana

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Introduction: Traumatic brain injury (TBI) is defined as the temporary or permanent alteration in brain function and pathology caused by an external mechanical force. It represents the leading cause of mortality and morbidity among children and youth individuals. Various models of TBI in rodents have been developed in the laboratory to mimic the scenario of injury. Blast overpressure injury is common among civilians and military personnel, followed by accidents or explosive devices. In addition to this, the lateral Controlled cortical impact (CCI) model mimics the blunt, penetrating injury. Method: In the present study, we have developed two different mild TBI models using blast and CCI injury. In the blast model, helium gas was used to create an overpressure of 130 kPa (±5) via a shock tube, and CCI injury was induced with an impact depth of 1.5mm to create diffusive and focal injury, respectively. C57BL/6J male mice (10-12 weeks) were divided into three groups: (1) control, (2) Blast treated, (3) CCI treated, and were exposed to different injury models. Serum was collected on Day1 and day7, followed by biphasic extraction using MTBE/Methanol/Water. Prepared samples were separated on Charged Surface Hybrid (CSH) C18 column and acquired on UHPLC-Q-TOF-MS using ESI probe with inhouse optimized parameters and method. MS peak list was generated using Markerview TM. Data were normalized, Pareto-scaled, and log-transformed, followed by multivariate and univariate analysis in metaboanalyst. Result and discussion: Untargeted profiling of lipids generated extensive data features, which were annotated through LIPID MAPS® based on their m/z and were further confirmed based on their fragment pattern by LipidBlast. There is the final annotation of 269 features in the positive and 182 features in the negative mode of ionization. PCA and PLS-DA score plots showed clear segregation of injury groups to controls. Among various lipids in mild blast and CCI, five lipids (Glycerophospholipids {PC 30:2, PE O-33:3, PG 28:3;O3 and PS 36:1 } and fatty acyl { FA 21:3;O2}) were significantly altered in both injury groups at Day 1 and Day 7, and also had VIP score >1. Pathway analysis by Biopan has also shown hampered synthesis of Glycerolipids and Glycerophospholipiods, which coincides with earlier reports. It could be a direct result of alteration in the Acetylcholine signaling pathway in response to TBI. Understanding the role of a specific class of lipid metabolism, regulation and transport could be beneficial to TBI research since it could provide new targets and determine the best therapeutic intervention. This study demonstrates the potential lipid biomarkers which can be used for injury severity diagnosis and identification irrespective of injury type (diffusive or focal).

Keywords: LipidBlast, lipidomic biomarker, LIPID MAPS®, TBI

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55 The Effects of Heavy Metal and Aromatic Hydrocarbon Pollution on Bees

Authors: Katarzyna Zięba, Hajnalka Szentgyörgyi, Paweł Miśkowiec, Agnieszka Moos-Matysik

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Bees are effective pollinators of plants using by humans. However, there is a concern about the fate different species due to their recently decline. Pollution of the environment is described in the literature as one of the causes of this phenomenon. Due to human activities, heavy metals and aromatic hydrocarbons can occur in bee organisms in high concentrations. The presented study aims to provide information on how pollution affects bee quality, taking into account, also the biological differences between various groups of bees. Understanding the consequences of environmental pollution on bees can help to create and promote bee friendly habitats and actions. The analyses were carried out using two contamination gradients with 5 sites on each. The first, mainly heavy metal polluted gradient is stretching approx. 30km from the Bukowno Zinc smelter near Olkusz in the Lesser Poland Voivodship, to the north. The second cuts through the agglomeration of Kraków up to the southern borders of the Ojców National Park. The gradient near Olkusz is a well-described pollution gradient contaminated mainly by zinc, lead, and cadmium. The second gradient cut through the agglomeration of Kraków and end below the Ojców National Park. On each gradient, two bee species were installed: red mason bees (Osmia bicornis) and honey bees (Apis mellifera). Red mason bee is a polylectic, solitary bee species, widely distributed in Poland. Honey bees are a highly social species of bees, with clearly defined casts and roles in the colony. Before installing the bees in the field, samples of imagos of red mason bees and samples of pollen and imagos from each honey bee colony were analysed for zinc, lead cadmium, polycyclic and monocyclic hydrocarbons levels. After collecting the bees from the field, samples of bees and pollen samples for each site were prepared for heavy metal, monocyclic hydrocarbon, and polycyclic hydrocarbon analysis. Analyses of aromatic hydrocarbons were performed with gas chromatography coupled with a headspace sampler (HP 7694E) and mass spectrometer (MS) as detector. Monocyclic compounds were injected into column with headspace sampler while polycyclic ones with manual injector (after solid-liquid extraction with hexane). The heavy metal content (zinc, lead and cadmium) was assessed with flame atomic absorption spectroscopy (FAAS AAnalyst 300 Perkin Elmer spectrometer) according to the methods for honey and bee products described in the literature. Pollution levels found in bee bodies and imago body masses in both species, and proportion of sex in case of red mason bees were correlated with pollution levels found in pollen for each site and colony or trap nest. An attempt to pinpoint the most important form of contamination regarding bee health was also be undertaken based on the achieved results.

Keywords: heavy metals, aromatic hydrocarbons, bees, pollution

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54 Production of Nanocomposite Electrical Contact Materials Ag-SnO2, W-Cu and Cu-C in Thermal Plasma

Authors: A. V. Samokhin, A. A. Fadeev, M. A. Sinaiskii, N. V. Alekseev, A. V. Kolesnikov

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Composite materials where metal matrix is reinforced by ceramic or metal particles are of great interest for use in the manufacturing of electrical contacts. Significant improvement of the composite physical and mechanical properties as well as increase of the performance parameters of composite-based products can be achieved if the nanoscale structure in the composite materials is obtained by using nanosized powders as starting components. The results of nanosized composite powders synthesis (Ag-SnO2, W-Cu and Cu-C) in the DC thermal plasma flows are presented in this paper. The investigations included the following processes: - Recondensation of micron powder mixture Ag + SnO2 in a nitrogen plasma; - The reduction of the oxide powders mixture (WO3 + CuO) in a hydrogen-nitrogen plasma; - Decomposition of the copper formate and copper acetate powders in nitrogen plasma. The calculations of equilibrium compositions of multicomponent systems Ag-Sn-O-N, W-Cu-O-H-N and Cu-O-C-H-N in the temperature range of 400-5000 K were carried to estimate basic process characteristics. Experimental studies of the processes were performed using a plasma reactor with a confined jet flow. The plasma jet net power was in the range of 2 - 13 kW, and the feedstock flow rate was up to 0.35 kg/h. The obtained powders were characterized by TEM, HR-TEM, SEM, EDS, ED-XRF, XRD, BET and QEA methods. Nanocomposite Ag-SnO2 (12 wt. %). Processing of the initial powder mixture (Ag-SnO2) in nitrogen thermal plasma stream allowed to produce nanopowders with a specific surface area up to 24 m2/g, consisting predominantly of particles with size less than 100 nm. According to XRD results, tin was present in the obtained products as SnO2 phase, and also as intermetallic phases AgxSn. Nanocomposite W-Cu (20 wt .%). Reduction of (WO3+CuO) mixture in the hydrogen-nitrogen plasma provides W-Cu nanopowder with particle sizes in the range of 10-150 nm. The particles have mainly spherical shape and structure tungsten core - copper shell. The thickness of the shell is about several nanometers, the shell is composed of copper and its oxides (Cu2O, CuO). The nanopowders had 1.5 wt. % oxygen impurity. Heat treatment in a hydrogen atmosphere allows to reduce the oxygen content to less than 0.1 wt. %. Nanocomposite Cu-C. Copper nanopowders were found as products of the starting copper compounds decomposition. The nanopowders primarily had a spherical shape with a particle size of less than 100 nm. The main phase was copper, with small amount of Cu2O and CuO oxides. Copper formate decomposition products had a specific surface area 2.5-7 m2/g and contained 0.15 - 4 wt. % carbon; and copper acetate decomposition products had the specific surface area 5-35 m2/g, and carbon content of 0.3 - 5 wt. %. Compacting of nanocomposites (sintering in hydrogen for Ag-SnO2 and electric spark sintering (SPS) for W-Cu) showed that the samples having a relative density of 97-98 % can be obtained with a submicron structure. The studies indicate the possibility of using high-intensity plasma processes to create new technologies to produce nanocomposite materials for electric contacts.

Keywords: electrical contact, material, nanocomposite, plasma, synthesis

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53 Investigation of Hydrate Formation of Associated Petroleum Gas From Promoter Solutions for the Purpose of Utilization and Reduction of Its Burning

Authors: Semenov Matvei, Stoporev Andrey, Pavelyev Roman, Varfolomeev Mikhail

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Gas hydrates are host-guest compounds. Guest molecules can be low molecular weight components of associated petroleum gas (C1-C4 hydrocarbons), carbon dioxide, hydrogen sulfide, and nitrogen. Gas hydrates have a number of unique properties that make them interesting from a technological point of view, for example, for storing hydrocarbon gases in solid form under moderate thermobaric conditions. The hydrate form of gas has a number of advantages, including a significant gas content in the hydrate, relative safety and environmental friendliness of the process. Such technology could be especially useful in cold regions, where hydrate production, storage and transportation can be more energy efficient. Recently, new developments have been proposed that seek to reduce the number of steps to obtain the finished hydrate, for example, using a pressing device/screw inside the reactor. However, the energy consumption required for the hydrate formation process remains a challenge. Thus, the goal of the current work is to study the patterns and mechanisms of the hydrate formation process using small additions of hydrate formation promoters under static conditions. The study of these aspects will help solve the problem of accelerated production of gas hydrates with minimal energy consumption. Currently, new compounds have been developed that can accelerate the formation of methane hydrate with a small amount of promoter in water, not exceeding 0.1% by weight. To test the influence of promoters on the process of hydrate formation, standard experiments are carried out under dynamic conditions with stirring. During such experiments, the time at which hydrate formation begins (induction period), the temperature at which formation begins (supercooling), the rate of hydrate formation, and the degree of conversion of water to hydrate are assessed. This approach helps to determine the most effective compound in comparative experiments with different promoters and select their optimal concentration. These experimental studies made it possible to study the features of the formation of associated petroleum gas hydrate from promoter solutions under static conditions. Phase transformations were studied using high-pressure micro-differential scanning calorimetry under various experimental conditions. Visual studies of the growth mode of methane hydrate depending on the type of promoter were also carried out. The work is an extension of the methodology for studying the effect of promoters on the process of associated petroleum gas hydrate formation in order to identify new ways to accelerate the formation of gas hydrates without the use of mixing. This work presents the results of a study of the process of associated petroleum gas hydrate formation using high-pressure differential scanning micro-calorimetry, visual investigation, gas chromatography, autoclaves study and stability data. It was found that the synthesized compounds multiply the conversion of water into hydrate under static conditions up to 96% due to a change in the growth mechanism of associated petroleum gas hydrate.

Keywords: gas hydrate, gas storage, promotor, associated petroleum gas

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52 Developing Granular Sludge and Maintaining High Nitrite Accumulation for Anammox to Treat Municipal Wastewater High-efficiently in a Flexible Two-stage Process

Authors: Zhihao Peng, Qiong Zhang, Xiyao Li, Yongzhen Peng

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Nowadays, conventional nitrogen removal process (nitrification and denitrification) was adopted in most wastewater treatment plants, but many problems have occurred, such as: high aeration energy consumption, extra carbon sources dosage and high sludge treatment costs. The emergence of anammox has bring about the great revolution to the nitrogen removal technology, and only the ammonia and nitrite were required to remove nitrogen autotrophically, no demand for aeration and sludge treatment. However, there existed many challenges in anammox applications: difficulty of biomass retention, insufficiency of nitrite substrate, damage from complex organic etc. Much effort was put into the research in overcoming the above challenges, and the payment was rewarded. It was also imperative to establish an innovative process that can settle the above problems synchronously, after all any obstacle above mentioned can cause the collapse of anammox system. Therefore, in this study, a two-stage process was established that the sequencing batch reactor (SBR) and upflow anaerobic sludge blanket (UASB) were used in the pre-stage and post-stage, respectively. The domestic wastewater entered into the SBR first and went through anaerobic/aerobic/anoxic (An/O/A) mode, and the draining at the aerobic end of SBR was mixed with domestic wastewater, the mixture then entering to the UASB. In the long term, organic and nitrogen removal performance was evaluated. All along the operation, most COD was removed in pre-stage (COD removal efficiency > 64.1%), including some macromolecular organic matter, like: tryptophan, tyrosinase and fulvic acid, which could weaken the damage of organic matter to anammox. And the An/O/A operating mode of SBR was beneficial to the achievement and maintenance of partial nitrification (PN). Hence, sufficient and steady nitrite supply was another favorable condition to anammox enhancement. Besides, the flexible mixing ratio helped to gain a substrate ratio appropriate to anammox (1.32-1.46), which further enhance the anammox. Further, the UASB was used and gas recirculation strategy was adopted in the post-stage, aiming to achieve granulation by the selection pressure. As expected, the granules formed rapidly during 38 days, which increased from 153.3 to 354.3 μm. Based on bioactivity and gene measurement, the anammox metabolism and abundance level rose evidently, by 2.35 mgN/gVss·h and 5.3 x109. The anammox bacteria mainly distributed in the large granules (>1000 μm), while the biomass in the flocs (<200 μm) and microgranules (200-500 μm) barely displayed anammox bioactivity. Enhanced anammox promoted the advanced autotrophic nitrogen removal, which increased from 71.9% to 93.4%, even when the temperature was only 12.9 ℃. Therefore, it was feasible to enhance anammox in the multiple favorable conditions created, and the strategy extended the application of anammox to the full-scale mainstream, enhanced the understanding of anammox in the aspects of culturing conditions.

Keywords: anammox, granules, nitrite accumulation, nitrogen removal efficiency

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51 Functional Switching of Serratia marcescens Transcriptional Regulator from Activator to Inhibitor of Quorum Sensing by Exogenous Addition

Authors: Norihiro Kato, Yuriko Takayama

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Some gram-negative bacteria enable the simultaneous activation of gene expression involved in N-acylhomoserine lactone (AHL) dependent cell-to-cell communication system. Such regulatory system for the bacterial group behavior is termed as quorum sensing (QS) because a diffusible AHL signal can accumulate around the cell during the increase of the cell density and trigger activation of the sequential QS process. By blocking the QS, the expression of diverse genes related to infection, antibiotic production, and biofilm formation is inhibited. Conditioning of QS by regulation of the DNA-receptor-AHL interaction is a potential target for enhancing host defenses against pathogenicity. We focused on engineered application of transcriptional regulator SpnR produced in opportunistic human pathogen Serratia marcescens. The SpnR can interact with AHL signals at an N-terminal domain and also with a promoter region of a QS target gene at a C-terminal domain. As the initial process of the QS activation, the SpnR forms a complex with the AHL to enhance the expression of pig cluster; the SpnR normally acts as an activator for the expression of the QS-dependent gene. In this research, we attempt to artificially control QS by changing the role of SpnR. The QS-dependent prodigiosin production is expected to inhibit by externally added SpnR in the culture broth of AS-1 strain because the AHL concentration was kept below the threshold by AHL-SpnR complex formation. Maltose-binding protein (MBP)-tagged SpnR (MBP-SpnR) was overexpressed in Escherichia coli and purified using an affinity chromatography equipped with an amylose resin column. The specific interaction between AHL and MBP-SpnR was demonstrated by quartz crystal microbalance (QCM) sensor. AHL with amino end-group was coupled with COOH-terminated self-assembled monolayer prepared on a gold electrode of 27-MHz quartz crystal sensor using water-soluble carbodiimide. After the injection of MBP-SpnR into a cup-type sensor cell filled with the buffer solution, time course of resonant frequency change (ΔFs) was determined. A decrease of ΔFs clearly showed the uptake of MBP-SpnR onto the AHL-immobilized electrode. Furthermore, no binding affinity was observed after the heat-inactivation of MBP-SpnR at 80ºC. These results suggest that MBP-SpnR possesses a specific affinity for AHL. MBP-SpnR was added to the culture medium as an AHL trap to study inhibitory effects on intracellularly accumulated prodigiosin. With approximately 2 µM MBP-SpnR, the amount of prodigiosin induced was half that of the control without any additives. In conclusion, the function of SpnR could be switched by adding it to the cell culture. Exogenously added MBP-SpnR possesses high affinity for AHL derived from cells and acts as an inhibitor of AHL-mediated QS.

Keywords: intracellular signaling, microbial biotechnology, quorum sensing, transcriptional regulator

Procedia PDF Downloads 241
50 Kinetic Evaluation of Sterically Hindered Amines under Partial Oxy-Combustion Conditions

Authors: Sara Camino, Fernando Vega, Mercedes Cano, Benito Navarrete, José A. Camino

Abstract:

Carbon capture and storage (CCS) technologies should play a relevant role towards low-carbon systems in the European Union by 2030. Partial oxy-combustion emerges as a promising CCS approach to mitigate anthropogenic CO₂ emissions. Its advantages respect to other CCS technologies rely on the production of a higher CO₂ concentrated flue gas than these provided by conventional air-firing processes. The presence of more CO₂ in the flue gas increases the driving force in the separation process and hence it might lead to further reductions of the energy requirements of the overall CO₂ capture process. A higher CO₂ concentrated flue gas should enhance the CO₂ capture by chemical absorption in solvent kinetic and CO₂ cyclic capacity. They have impact on the performance of the overall CO₂ absorption process by reducing the solvent flow-rate required for a specific CO₂ removal efficiency. Lower solvent flow-rates decreases the reboiler duty during the regeneration stage and also reduces the equipment size and pumping costs. Moreover, R&D activities in this field are focused on novel solvents and blends that provide lower CO₂ absorption enthalpies and therefore lower energy penalties associated to the solvent regeneration. In this respect, sterically hindered amines are considered potential solvents for CO₂ capture. They provide a low energy requirement during the regeneration process due to its molecular structure. However, its absorption kinetics are slow and they must be promoted by blending with faster solvents such as monoethanolamine (MEA) and piperazine (PZ). In this work, the kinetic behavior of two sterically hindered amines were studied under partial oxy-combustion conditions and compared with MEA. A lab-scale semi-batch reactor was used. The CO₂ composition of the synthetic flue gas varied from 15%v/v – conventional coal combustion – to 60%v/v – maximum CO₂ concentration allowable for an optimal partial oxy-combustion operation. Firstly, 2-amino-2-methyl-1-propanol (AMP) showed a hybrid behavior with fast kinetics and a low enthalpy of CO₂ absorption. The second solvent was Isophrondiamine (IF), which has a steric hindrance in one of the amino groups. Its free amino group increases its cyclic capacity. In general, the presence of higher CO₂ concentration in the flue gas accelerated the CO₂ absorption phenomena, producing higher CO₂ absorption rates. In addition, the evolution of the CO2 loading also exhibited higher values in the experiments using higher CO₂ concentrated flue gas. The steric hindrance causes a hybrid behavior in this solvent, between both fast and slow kinetic solvents. The kinetics rates observed in all the experiments carried out using AMP were higher than MEA, but lower than the IF. The kinetic enhancement experienced by AMP at a high CO2 concentration is slightly over 60%, instead of 70% – 80% for IF. AMP also improved its CO₂ absorption capacity by 24.7%, from 15%v/v to 60%v/v, almost double the improvements achieved by MEA. In IF experiments, the CO₂ loading increased around 10% from 15%v/v to 60%v/v CO₂ and it changed from 1.10 to 1.34 mole CO₂ per mole solvent, more than 20% of increase. This hybrid kinetic behavior makes AMP and IF promising solvents for partial oxy–combustion applications.

Keywords: absorption, carbon capture, partial oxy-combustion, solvent

Procedia PDF Downloads 162
49 Iron Oxide Reduction Using Solar Concentration and Carbon-Free Reducers

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

Procedia PDF Downloads 106
48 Effect of Ion Irradiation on the Microstructure and Properties of Chromium Coatings on Zircaloy-4 Substrate

Authors: Alexia Wu, Joel Ribis, Jean-Christophe Brachet, Emmanuel Clouet, Benoit Arnal, Elodie Rouesne, Stéphane Urvoy, Justine Roubaud, Yves Serruys, Frederic Lepretre

Abstract:

To enhance the safety of Light Water Reactor, accident tolerant fuel (ATF) claddings materials are under development. In the framework of CEA-AREVA-EDF collaborative program on ATF cladding materials, CEA has engaged specific studies on chromium coated zirconium alloys. Especially for Loss-of-Coolant-Accident situations, chromium coated claddings have shown some additional 'coping' time before achieving full embrittlement of the oxidized cladding, when compared to uncoated references – both tested in steam environment up to 1300°C. Nevertheless, the behavior of chromium coatings and the stability of the Zr-Cr interface under neutron irradiation remain unknown. Two main points are addressed: 1. Bulk Cr behavior under irradiation: Due to its BCC crystallographic structure, Cr is prone to Ductile-to-Brittle-Transition at quite high temperature. Irradiation could be responsible for a significant additional DBTT shift towards higher temperatures. 2. Zircaloy/Cr interface behavior under irradiation: Preliminary TEM examinations of un-irradiated samples revealed a singular Zircaloy-4/Cr interface with nanometric intermetallic phase layers. Such particular interfaces highlight questions of how they would behave under irradiation - intermetallic zirconium phases are known to be more or less stable under irradiations. Another concern is a potential enhancement of chromium diffusion into the zirconium-alpha based substrate. The purpose of this study is then to determine the behavior of such coatings after ion irradiations, as a surrogate to neutron irradiation. Ion irradiations were performed at the Jannus-Saclay facility (France). 20 MeV Kr8+ ions at 400°C with a flux of 2.8x1011 ions.cm-2.s-1 were used to irradiate chromium coatings of 1-2 µm thick on Zircaloy-4 sheets substrate. At the interface, the calculated damage is close to 10 dpa (SRIM, Quick Calculation Damage mode). Thin foil samples were prepared with FIB for both as-received and irradiated coated samples. Transmission Electron Microscopy (TEM) and in-situ tensile tests in a Scanning Electron Microscope are being used to characterize the un-irradiated and irradiated materials. High Resolution TEM highlights a great complexity of the interface before irradiation since it is formed of an alternation of intermetallic phases – C14 and C15. The interfaces formed by these intermetallic phases with chromium and zirconium show semi-coherency. Chemical analysis performed before irradiation shows some iron enrichment at the interface. The chromium coating bulk microstructures and properties are also studied before and after irradiation. On-going in-situ tensile tests focus on the capacity of chromium coatings to sustain some plastic deformation when tested up to 350°C. The stability of the Cr/Zr interface is shown after ion irradiation up to 10 dpa. This observation constitutes the first result after irradiation on these new coated claddings materials.

Keywords: accident tolerant fuel, HRTEM, interface, ion-irradiation

Procedia PDF Downloads 335
47 Seismic Assessment of Flat Slab and Conventional Slab System for Irregular Building Equipped with Shear Wall

Authors: Muhammad Aji Fajari, Ririt Aprilin Sumarsono

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Particular instability of structural building under lateral load (e.g earthquake) will rise due to irregularity in vertical and horizontal direction as stated in SNI 03-1762-2012. The conventional slab has been considered for its less contribution in increasing the stability of the structure, except special slab system such as flat slab turned into account. In this paper, the analysis of flat slab system at Sequis Tower located in South Jakarta will be assessed its performance under earthquake. It consists of 6 floors of the basement where the flat slab system is applied. The flat slab system will be the main focus in this paper to be compared for its performance with conventional slab system under earthquake. Regarding the floor plan of Sequis Tower basement, re-entrant corner signed for this building is 43.21% which exceeded the allowable re-entrant corner is 15% as stated in ASCE 7-05 Based on that, the horizontal irregularity will be another concern for analysis, otherwise vertical irregularity does not exist for this building. Flat slab system is a system where the slabs use drop panel with shear head as their support instead of using beams. Major advantages of flat slab application are decreasing dead load of structure, removing beams so that the clear height can be maximized, and providing lateral resistance due to lateral load. Whilst, deflection at middle strip and punching shear are problems to be detail considered. Torsion usually appears when the structural member under flexure such as beam or column dimension is improper in ratio. Considering flat slab as alternative slab system will keep the collapse due to torsion down. Common seismic load resisting system applied in the building is a shear wall. Installation of shear wall will keep the structural system stronger and stiffer affecting in reduced displacement under earthquake. Eccentricity of shear wall location of this building resolved the instability due to horizontal irregularity so that the earthquake load can be absorbed. Performing linear dynamic analysis such as response spectrum and time history analysis due to earthquake load is suitable as the irregularity arise so that the performance of structure can be significantly observed. Utilization of response spectrum data for South Jakarta which PGA 0.389g is basic for the earthquake load idealization to be involved in several load combinations stated on SNI 03-1726-2012. The analysis will result in some basic seismic parameters such as period, displacement, and base shear of the system; besides the internal forces of the critical member will be presented. Predicted period of a structure under earthquake load is 0.45 second, but as different slab system applied in the analysis then the period will show a different value. Flat slab system will probably result in better performance for the displacement parameter compare to conventional slab system due to higher contribution of stiffness to the whole system of the building. In line with displacement, the deflection of the slab will result smaller for flat slab than a conventional slab. Henceforth, shear wall will be effective to strengthen the conventional slab system than flat slab system.

Keywords: conventional slab, flat slab, horizontal irregularity, response spectrum, shear wall

Procedia PDF Downloads 166
46 Hydrogen Production from Auto-Thermal Reforming of Ethanol Catalyzed by Tri-Metallic Catalyst

Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

Procedia PDF Downloads 124
45 Fischer Tropsch Synthesis in Compressed Carbon Dioxide with Integrated Recycle

Authors: Kanchan Mondal, Adam Sims, Madhav Soti, Jitendra Gautam, David Carron

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Fischer-Tropsch (FT) synthesis is a complex series of heterogeneous reactions between CO and H2 molecules (present in the syngas) on the surface of an active catalyst (Co, Fe, Ru, Ni, etc.) to produce gaseous, liquid, and waxy hydrocarbons. This product is composed of paraffins, olefins, and oxygenated compounds. The key challenge in applying the Fischer-Tropsch process to produce transportation fuels is to make the capital and production costs economically feasible relative to the comparative cost of existing petroleum resources. To meet this challenge, it is imperative to enhance the CO conversion while maximizing carbon selectivity towards the desired liquid hydrocarbon ranges (i.e. reduction in CH4 and CO2 selectivities) at high throughputs. At the same time, it is equally essential to increase the catalyst robustness and longevity without sacrificing catalyst activity. This paper focuses on process development to achieve the above. The paper describes the influence of operating parameters on Fischer Tropsch synthesis (FTS) from coal derived syngas in supercritical carbon dioxide (ScCO2). In addition, the unreacted gas and solvent recycle was incorporated and the effect of unreacted feed recycle was evaluated. It was expected that with the recycle, the feed rate can be increased. The increase in conversion and liquid selectivity accompanied by the production of narrower carbon number distribution in the product suggest that higher flow rates can and should be used when incorporating exit gas recycle. It was observed that this process was capable of enhancing the hydrocarbon selectivity (nearly 98 % CO conversion), reducing improving the carbon efficiency from 17 % to 51 % in a once through process and further converting 16 % CO2 to liquid with integrated recycle of the product gas stream and increasing the life of the catalyst. Catalyst robustness enhancement has been attributed to the absorption of heat of reaction by the compressed CO2 which reduced the formation of hotspots and the dissolution of waxes by the CO2 solvent which reduced the blinding of active sites. In addition, the recycling the product gas stream reduced the reactor footprint to one-fourth of the once through size and product fractionation utilizing the solvent effects of supercritical CO2 were realized. In addition to the negative CO2 selectivities, methane production was also inhibited and was limited to less than 1.5%. The effect of the process conditions on the life of the catalysts will also be presented. Fe based catalysts are known to have a high proclivity for producing CO2 during FTS. The data of the product spectrum and selectivity on Co and Fe-Co based catalysts as well as those obtained from commercial sources will also be presented. The measurable decision criteria were the increase in CO conversion at H2:CO ratio of 1:1 (as commonly found in coal gasification product stream) in supercritical phase as compared to gas phase reaction, decrease in CO2 and CH4 selectivity, overall liquid product distribution, and finally an increase in the life of the catalysts.

Keywords: carbon efficiency, Fischer Tropsch synthesis, low GHG, pressure tunable fractionation

Procedia PDF Downloads 216
44 Identification and Understanding of Colloidal Destabilization Mechanisms in Geothermal Processes

Authors: Ines Raies, Eric Kohler, Marc Fleury, Béatrice Ledésert

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In this work, the impact of clay minerals on the formation damage of sandstone reservoirs is studied to provide a better understanding of the problem of deep geothermal reservoir permeability reduction due to fine particle dispersion and migration. In some situations, despite the presence of filters in the geothermal loop at the surface, particles smaller than the filter size (<1 µm) may surprisingly generate significant permeability reduction affecting in the long term the overall performance of the geothermal system. Our study is carried out on cores from a Triassic reservoir in the Paris Basin (Feigneux, 60 km Northeast of Paris). Our goal is to first identify the clays responsible for clogging, a mineralogical characterization of these natural samples was carried out by coupling X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The results show that the studied stratigraphic interval contains mostly illite and chlorite particles. Moreover, the spatial arrangement of the clays in the rocks as well as the morphology and size of the particles, suggest that illite is more easily mobilized than chlorite by the flow in the pore network. Thus, based on these results, illite particles were prepared and used in core flooding in order to better understand the factors leading to the aggregation and deposition of this type of clay particles in geothermal reservoirs under various physicochemical and hydrodynamic conditions. First, the stability of illite suspensions under geothermal conditions has been investigated using different characterization techniques, including Dynamic Light Scattering (DLS) and Scanning Transmission Electron Microscopy (STEM). Various parameters such as the hydrodynamic radius (around 100 nm), the morphology and surface area of aggregates were measured. Then, core-flooding experiments were carried out using sand columns to mimic the permeability decline due to the injection of illite-containing fluids in sandstone reservoirs. In particular, the effects of ionic strength, temperature, particle concentration and flow rate of the injected fluid were investigated. When the ionic strength increases, a permeability decline of more than a factor of 2 could be observed for pore velocities representative of in-situ conditions. Further details of the retention of particles in the columns were obtained from Magnetic Resonance Imaging and X-ray Tomography techniques, showing that the particle deposition is nonuniform along the column. It is clearly shown that very fine particles as small as 100 nm can generate significant permeability reduction under specific conditions in high permeability porous media representative of the Triassic reservoirs of the Paris basin. These retention mechanisms are explained in the general framework of the DLVO theory

Keywords: geothermal energy, reinjection, clays, colloids, retention, porosity, permeability decline, clogging, characterization, XRD, SEM-EDS, STEM, DLS, NMR, core flooding experiments

Procedia PDF Downloads 144
43 Laboratory Assessment of Electrical Vertical Drains in Composite Soils Using Kaolin and Bentonite Clays

Authors: Maher Z. Mohammed, Barry G. Clarke

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As an alternative to stone column in fine grained soils, it is possible to create stiffened columns of soils using electroosmosis (electroosmotic piles). This program of this research is to establish the effectiveness and efficiency of the process in different soils. The aim of this study is to assess the capability of electroosmosis treatment in a range of composite soils. The combined electroosmotic and preloading equipment developed by Nizar and Clarke (2013) was used with an octagonal array of anodes surrounding a single cathode in a nominal 250mm diameter 300mm deep cylinder of soil and 80mm anode to cathode distance. Copper coiled springs were used as electrodes to allow the soil to consolidate either due to an external vertical applied load or electroosmosis. The equipment was modified to allow the temperature to be monitored during the test. Electroosmotic tests were performed on China Clay Grade E kaolin and calcium bentonite (Bentonex CB) mixed with sand fraction C (BS 1881 part 131) at different ratios by weight; (0, 23, 33, 50 and 67%) subjected to applied voltages (5, 10, 15 and 20). The soil slurry was prepared by mixing the dry soil with water to 1.5 times the liquid limit of the soil mixture. The mineralogical and geotechnical properties of the tested soils were measured before the electroosmosis treatment began. In the electroosmosis cell tests, the settlement, expelled water, variation of electrical current and applied voltage, and the generated heat was monitored during the test time for 24 osmotic tests. Water content was measured at the end of each test. The electroosmotic tests are divided into three phases. In Phase 1, 15 kPa was applied to simulate a working platform and produce a uniform soil which had been deposited as a slurry. 50 kPa was used in Phase 3 to simulate a surcharge load. The electroosmotic treatment was only performed during Phase 2 where a constant voltage was applied through the electrodes in addition to the 15 kPa pressure. This phase was stopped when no further water was expelled from the cell, indicating the electroosmotic process had stopped due to either the degradation of the anode or the flow due to the hydraulic gradient exactly balanced the electroosmotic flow resulting in no flow. Control tests for each soil mixture were carried out to assess the behaviour of the soil samples subjected to only an increase of vertical pressure, which is 15kPa in Phase 1 and 50kPa in Phase 3. Analysis of the experimental results from this study showed a significant dewatering effect on the soil slurries. The water discharged by the electroosmotic treatment process decreased as the sand content increased. Soil temperature increased significantly when electrical power was applied and drops when applied DC power turned off or when the electrode degraded. The highest increase in temperature was found in pure clays at higher applied voltage after about 8 hours of electroosmosis test.

Keywords: electrokinetic treatment, electrical conductivity, electroosmotic consolidation, electroosmosis permeability ratio

Procedia PDF Downloads 131
42 Ammonia Cracking: Catalysts and Process Configurations for Enhanced Performance

Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

Procedia PDF Downloads 34
41 Isolation and Structural Elucidation of 20 Hydroxyecdystone from Vitex doniana Sweet Stem Bark

Authors: Mustapha A. Tijjani, Fanna I. Abdulrahman, Irfan Z. Khan, Umar K. Sandabe, Cong Li

Abstract:

Air dried sample V. doniana after collection and identification was extracted with ethanol and further partition with chloroform, ethyl acetate and n-butanol. Ethanolic extract (11.9g) was fractionated on a silica gel accelerated column chromatography using solvents such as n-hexane, ethyl acetate and methanol. Each eluent fractions (150ml aliquots) were collected and monitored with thin layer chromatography. Fractions with similar Rf values from same solvents system were pooled together. Phytochemical test of all the fractions were performed using standard procedure. Complete elution yielded 48 fractions (150ml/fraction) which were pooled to 24 fractions base on the Rf values. It was further recombined and 12 fractions were obtained on the basis on Rf values and coded Vd1 to Vd12 fractions. Vd8 was further eluted with ethylacetate and methanol and gave fourteen sub fractions Vd8-a, -Vd8-m. Fraction Vd8-a (56mg) gave a white crystal compound coded V1. It was further checked on TLC and observed under ultraviolet lamp and was found to give a single spot. The Rf values were calculated to be 0.433. The melting point was determined using Gallenkamp capillary melting point apparatus and found to be 241-243°C uncorrected. Characterization of the isolated compound coded V1 was done using FT-infra-red spectroscopy, HNMR, 13CNMR(1and 2D) and HRESI-MS. The IR spectrum of compound V1 shows prominent peaks that corresponds to OHstr (3365cm-1) and C=0 (1652cm-1) etc. This spectrum suggests that among the functional moiety in compound V1 are the carbonyl and hydroxyl group. The 1H NMR (400 MHz) spectrum of compound V1 in DMSO-d6 displayed five singlet signals at δ 0.72 (3H, s, H-18), 0.79 (3H, s, H-19), 1.03 (3H, s, H-21), 1.04 (3H, s, H-26), 1.06 (3H, s, H-27) each integrating for three protons indicating the five methyl functional groups present in the compound. It further showed a broad singlet at δ 5.58 integrated for 1 H due to an olefinic H-atom adjacent to the carbonyl carbon atom. Three signals at δ 3.10 (d, J = 9.0 Hz, H-22), 3.59 (m, 1H, 2H-a) and 3.72 (m, 1H, 3H-e), each integrating for one proton is due to oxymethine protons indicating that three oxymethine H-atoms are present in the compound. These all signals are characteristic to the ecdysteroid skeletons. The 13C-NMR spectrum showed the presence of 27 carbon atoms, suggesting that may be steroid skeleton. The DEPT-135 experiment showed the presence of five CH3, eight CH2, and seven CH groups, and seven quaternary C-atoms. The molecular formula was established as C27H44O7 by high resolution electron spray ionization-mass spectroscopy (HRESI-MS) positive ion mode m/z 481.3179. The signals in mass spectrum are 463, 445, and 427 peaks corresponding to losses of one, two, three, or four water molecules characteristic for ecdysterone skeleton reported in the literature. Based on the spectral analysis (HNMR, 13CNMR, DEPT, HMQC, IR, HRESI-MS) the compound V1 is thus concluded to have ecdysteriod skeleton and conclusively conforms with 2β, 3β 14α, 20R, 22R, 25-hexahydroxy-5 β cholest-7-ene-6- one, or 2, 3, 14, 20, 22, 25 hexahydroxy cholest-7-ene-6-one commonly known as 20-hydroxyecdysone.

Keywords: vitex, phytochemical, purification, isolation, chromatography, spectroscopy

Procedia PDF Downloads 325
40 Photo-Fenton Degradation of Organic Compounds by Iron(II)-Embedded Composites

Authors: Marius Sebastian Secula, Andreea Vajda, Benoit Cagnon, Ioan Mamaliga

Abstract:

One of the most important classes of pollutants is represented by dyes. The synthetic character and complex molecular structure make them more stable and difficult to be biodegraded in water. The treatment of wastewaters containing dyes in order to separate/degrade dyes is of major importance. Various techniques have been employed to remove and/or degrade dyes in water. Advanced oxidation processes (AOPs) are known as among the most efficient ones towards dye degradation. The aim of this work is to investigate the efficiency of a cheap Iron-impregnated activated carbon Fenton-like catalyst in order to degrade organic compounds in aqueous solutions. In the presented study an anionic dye, Indigo Carmine, is considered as a model pollutant. Various AOPs are evaluated for the degradation of Indigo Carmine to establish the effect of the prepared catalyst. It was found that the Iron(II)-embedded activated carbon composite enhances significantly the degradation process of Indigo Carmine. Using the wet impregnation procedure, 5 g of L27 AC material were contacted with Fe(II) solutions of FeSO4 precursor at a theoretical iron content in the resulted composite of 1 %. The L27 AC was impregnated for 3h at 45°C, then filtered, washed several times with water and ethanol and dried at 55 °C for 24 h. Thermogravimetric analysis, Fourier transform infrared, X-ray diffraction, and transmission electron microscopy were employed to investigate the structural, textural, and micromorphology of the catalyst. Total iron content in the obtained composites and iron leakage were determined by spectrophotometric method using phenantroline. Photo-catalytic tests were performed using an UV - Consulting Peschl Laboratory Reactor System. UV light irradiation tests were carried out to determine the performance of the prepared Iron-impregnated composite towards the degradation of Indigo Carmine in aqueous solution using different conditions (17 W UV lamps, with and without in-situ generation of O3; different concentrations of H2O2, different initial concentrations of Indigo Carmine, different values of pH, different doses of NH4-OH enhancer). The photocatalytic tests were performed after the adsorption equilibrium has been established. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. The investigated process obeys the pseudo-first order kinetics. The photo-Fenton degradation of IC was tested at different values of initial concentration. The obtained results emphasize an enhancement of Indigo Carmine degradation in case of the heterogeneous photo-Fenton process conducted with an O3 generating UV lamp in the presence of hydrogen peroxide. Acknowledgments: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: photodegradation, heterogeneous Fenton, anionic dye, carbonaceous composite, screening factorial design

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39 Preparation of Biodegradable Methacrylic Nanoparticles by Semicontinuous Heterophase Polymerization for Drugs Loading: The Case of Acetylsalicylic Acid

Authors: J. Roberto Lopez, Hened Saade, Graciela Morales, Javier Enriquez, Raul G. Lopez

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Implementation of systems based on nanostructures for drug delivery applications have taken relevance in recent studies focused on biomedical applications. Although there are several nanostructures as drugs carriers, the use of polymeric nanoparticles (PNP) has been widely studied for this purpose, however, the main issue for these nanostructures is the size control below 50 nm with a narrow distribution size, due to they must go through different physiological barriers and avoid to be filtered by kidneys (< 10 nm) or the spleen (> 100 nm). Thus, considering these and other factors, it can be mentioned that drug-loaded nanostructures with sizes varying between 10 and 50 nm are preferred in the development and study of PNP/drugs systems. In this sense, the Semicontinuous Heterophase Polymerization (SHP) offers the possibility to obtain PNP in the desired size range. Considering the above explained, methacrylic copolymer nanoparticles were obtained under SHP. The reactions were carried out in a jacketed glass reactor with the required quantities of water, ammonium persulfate as initiator, sodium dodecyl sulfate/sodium dioctyl sulfosuccinate as surfactants, methyl methacrylate and methacrylic acid as monomers with molar ratio of 2/1, respectively. The monomer solution was dosed dropwise during reaction at 70 °C with a mechanical stirring of 650 rpm. Nanoparticles of poly(methyl methacrylate-co-methacrylic acid) were loaded with acetylsalicylic acid (ASA, aspirin) by a chemical adsorption technique. The purified latex was put in contact with a solution of ASA in dichloromethane (DCM) at 0.1, 0.2, 0.4 or 0.6 wt-%, at 35°C during 12 hours. According to the boiling point of DCM, as well as DCM and water densities, the loading process is completed when the whole DCM is evaporated. The hydrodynamic diameter was measured after polymerization by quasi-elastic light scattering and transmission electron microscopy, before and after loading procedures with ASA. The quantitative and qualitative analyses of PNP loaded with ASA were measured by infrared spectroscopy, differential scattering calorimetry and thermogravimetric analysis. Also, the molar mass distributions of polymers were determined in a gel permeation chromatograph apparatus. The load capacity and efficiency were determined by gravimetric analysis. The hydrodynamic diameter results for methacrylic PNP without ASA showed a narrow distribution with an average particle size around 10 nm and a composition methyl methacrylate/methacrylic acid molar ratio equal to 2/1, same composition of Eudragit S100, which is a commercial compound widely used as excipient. Moreover, the latex was stabilized in a relative high solids content (around 11 %), a monomer conversion almost 95 % and a number molecular weight around 400 Kg/mol. The average particle size in the PNP/aspirin systems fluctuated between 18 and 24 nm depending on the initial percentage of aspirin in the loading process, being the drug content as high as 24 % with an efficiency loading of 36 %. These average sizes results have not been reported in the literature, thus, the methacrylic nanoparticles here reported are capable to be loaded with a considerable amount of ASA and be used as a drug carrier.

Keywords: aspirin, biocompatibility, biodegradable, Eudragit S100, methacrylic nanoparticles

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38 Sonication as a Versatile Tool for Photocatalysts’ Synthesis and Intensification of Flow Photocatalytic Processes Within the Lignocellulose Valorization Concept

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

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

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

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37 Isoflavonoid Dynamic Variation in Red Clover Genotypes

Authors: Andrés Quiroz, Emilio Hormazábal, Ana Mutis, Fernando Ortega, Loreto Méndez, Leonardo Parra

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Red clover root borer, Hylastinus obscurus Marsham (Coleoptera: Curculionidae), is the main insect pest associated to red clover, Trifolium pratense L. An average of 1.5 H. obscurus per plant can cause 5.5% reduction in forage yield in pastures of two to three years old. Moreover, insect attack can reach 70% to 100% of the plants. To our knowledge, there is no a chemical strategy for controlling this pest. Therefore alternative strategies for controlling H. obscurus are a high priority for red clover producers. One of this alternative is related to the study of secondary metabolites involved in intrinsic chemical defenses developed by plants, such as isoflavonoids. The isoflavonoids formononetin and daidzein have elicited an antifeedant and phagostimult effect on H. obscurus respectively. However, we do not know how is the dynamic variation of these isoflavonoids under field conditions. The main objective of this work was to evaluate the variation of the antifeedant isoflavonoids formononetin, the phagostimulant isoflavonoids daidzein, and their respective glycosides over time in different ecotypes of red clover. Fourteen red clover ecotypes (8 cultivars and 6 experimental lines), were collected at INIA-Carillanca (La Araucanía, Chile). These plants were established in October 2015 under irrigated conditions. The cultivars were distributed in a randomized complete block with three replicates. The whole plants were sampled in four times: 15th October 2016, 12th December 2016, 27th January 2017 and 16th March 2017 with sufficient amount of soil to avoid root damage. A polar fraction of isoflavonoid was obtained from 20 mg of lyophilized root tissue extracted with 2 mL of 80% MeOH for 16 h using an orbital shaker in the dark at room temperature. After, an aliquot of 1.4 mL of the supernatant was evaporated, and the residue was resuspended in 300 µL of 45% MeOH. The identification and quantification of isoflavonoid root extracts were performed by the injection of 20 µL into a Shimadzu HPLC equipped with a C-18 column. The sample was eluted with a mobile phase composed of AcOH: H₂O (1:9 v/v) as solvent A and CH₃CN as solvent B. The detection was performed at 260 nm. The results showed that the amount of aglycones was higher than the respective glycosides. This result is according to the biosynthetic pathway of flavonoids, where the formation of glycoside is further to the glycosides biosynthesis. The amount of formononetin was higher than daidzein. In roots, where H. obscurus spent the most part of its live cycle, the highest content of formononetin was found in G 27, Pawera, Sabtoron High, Redqueli-INIA and Superqueli-INIA cvs. (2.1, 1.8, 1.8, 1.6 and 1.0 mg g⁻¹ respectively); and the lowest amount of daidzein were found Superqueli-INIA (0.32 mg g⁻¹) and in the experimental line Sel Syn Int4 (0.24 mg g⁻¹). This ecotype showed a high content of formononetin (0.9 mg g⁻¹). This information, associated with cultural practices, could help farmers and breeders to reduce H. obscurus in grassland, selecting ecotypes with high content of formononetin and low amount of daidzein in the roots of red clover plants. Acknowledgements: FONDECYT 1141245 and 11130715.

Keywords: daidzein, formononetin, isoflavonoid glycosides, trifolium pratense

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36 Enzymatic Determination of Limonene in Red Clover Genotypes

Authors: Andrés Quiroz, Emilio Hormazabal, Ana Mutis, Fernando Ortega, Manuel Chacón-Fuentes, Leonardo Parra

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Red clover (Trifolium pratense L.) is an important forage species in temperate regions of the world. The main limitation of this species worldwide is a lack of persistence related to the high mortality of plants due to a complex of biotic and abiotic factors, determining a life span of two or three seasons. Because of the importance of red clover in Chile, a red clover breeding program was started at INIA Carillanca Research Center in 1989, with the main objective of improving the survival of plants, forage yield, and persistence. The main selection criteria for selecting new varieties have been based on agronomical parameters and biotic factors. The main biotic factor associated with red clover mortality in Chile is Hylastinus obscurus (Coleoptera: Curculionidae). Both larval and adults feed on the roots, causing weakening and subsequent death of clover plants. Pesticides have not been successful for controlling infestations of this root borer. Therefore, alternative strategies for controlling this pest are a high priority for red clover producers. Currently, the role of semiochemical in the interaction between H. obscurus and red clover plants has been widely studied for our group. Specifically, from the red clover foliage has been identified limonene is eliciting repellency from the root borer. Limonene is generated in the plant from two independent biosynthetic pathways, the mevalonic acid, and deoxyxylulose pathway. Mevalonate pathway enzymes are localized in the cytosol, whereas the deoxyxylulose phosphate pathway enzymes are found in plastids. In summary, limonene can be determinated by enzymatic bioassay using GPP as substrate and by limonene synthase expression. Therefore, the main objective of this work was to study genetic variation of limonene in material provided by INIA´s Red Clover breeding program. Protein extraction was carried out homogenizing 250 mg of leave tissue and suspended in 6 mL of extraction buffer (PEG 1500, PVP-30, 20 mM MgCl2 and antioxidants) and stirred on ice for 20 min. After centrifugation, aliquots of 2.5 mL were desalted on PD-10 columns, resulting in a final volume of 3.5 mL. Protein determination was performed according to Bradford with BSA as a standard. Monoterpene synthase assays were performed with 50 µL of protein extracts transferred into gas-tight 2 mL crimp seal vials after addition of 4 µL MgCl₂ and 41 µL assay buffer. The assay was started by adding 5 µL of a GPP solution. The mixture was incubated for 30 min at 40 °C. Biosynthesized limonene was quantified in a GC equipped with a chiral column and using synthetic R and S-limonene standards. The enzymatic the production of R and S-limonene from different Superqueli-Carillanca genotypes is shown in this work. Preliminary results showed significant differences in limonene content among the genotypes analyzed. These results constitute an important base for selecting genotypes with a high content of this repellent monoterpene towards H. obscurus.

Keywords: head space, limonene enzymatic determination, red clover, Hylastinus obscurus

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35 Isolation and Characterization of a Narrow-Host Range Aeromonas hydrophila Lytic Bacteriophage

Authors: Sumeet Rai, Anuj Tyagi, B. T. Naveen Kumar, Shubhkaramjeet Kaur, Niraj K. Singh

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Since their discovery, indiscriminate use of antibiotics in human, veterinary and aquaculture systems has resulted in global emergence/spread of multidrug-resistant bacterial pathogens. Thus, the need for alternative approaches to control bacterial infections has become utmost important. High selectivity/specificity of bacteriophages (phages) permits the targeting of specific bacteria without affecting the desirable flora. In this study, a lytic phage (Ahp1) specific to Aeromonas hydrophila subsp. hydrophila was isolated from finfish aquaculture pond. The host range of Ahp1 range was tested against 10 isolates of A. hydrophila, 7 isolates of A. veronii, 25 Vibrio cholerae isolates, 4 V. parahaemolyticus isolates and one isolate each of V. harveyi and Salmonella enterica collected previously. Except the host A. hydrophila subsp. hydrophila strain, no lytic activity against any other bacterial was detected. During the adsorption rate and one-step growth curve analysis, 69.7% of phage particles were able to get adsorbed on host cell followed by the release of 93 ± 6 phage progenies per host cell after a latent period of ~30 min. Phage nucleic acid was extracted by column purification methods. After determining the nature of phage nucleic acid as dsDNA, phage genome was subjected to next-generation sequencing by generating paired-end (PE, 2 x 300bp) reads on Illumina MiSeq system. De novo assembly of sequencing reads generated circular phage genome of 42,439 bp with G+C content of 58.95%. During open read frame (ORF) prediction and annotation, 22 ORFs (out of 49 total predicted ORFs) were functionally annotated and rest encoded for hypothetical proteins. Proteins involved in major functions such as phage structure formation and packaging, DNA replication and repair, DNA transcription and host cell lysis were encoded by the phage genome. The complete genome sequence of Ahp1 along with gene annotation was submitted to NCBI GenBank (accession number MF683623). Stability of Ahp1 preparations at storage temperatures of 4 °C, 30 °C, and 40 °C was studied over a period of 9 months. At 40 °C storage, phage counts declined by 4 log units within one month; with a total loss of viability after 2 months. At 30 °C temperature, phage preparation was stable for < 5 months. On the other hand, phage counts decreased by only 2 log units over a period of 9 during storage at 4 °C. As some of the phages have also been reported as glycerol sensitive, the stability of Ahp1 preparations in (0%, 15%, 30% and 45%) glycerol stocks were also studied during storage at -80 °C over a period of 9 months. The phage counts decreased only by 2 log units during storage, and no significant difference in phage counts was observed at different concentrations of glycerol. The Ahp1 phage discovered in our study had a very narrow host range and it may be useful for phage typing applications. Moreover, the endolysin and holin genes in Ahp1 genome could be ideal candidates for recombinant cloning and expression of antimicrobial proteins.

Keywords: Aeromonas hydrophila, endolysin, phage, narrow host range

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34 Seismic Analysis of Vertical Expansion Hybrid Structure by Response Spectrum Method Concern with Disaster Management and Solving the Problems of Urbanization

Authors: Gautam, Gurcharan Singh, Mandeep Kaur, Yogesh Aggarwal, Sanjeev Naval

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The present ground reality scenario of suffering of humanity shows the evidence of failure to take wrong decisions to shape the civilization with Irresponsibilities in the history. A strong positive will of right responsibilities make the right civilization structure which affects itself and the whole world. Present suffering of humanity shows and reflect the failure of past decisions taken to shape the true culture with right social structure of society, due to unplanned system of Indian civilization and its rapid disaster of population make the failure to face all kind of problems which make the society sufferer. Our India is still suffering from disaster like earthquake, floods, droughts, tsunamis etc. and we face the uncountable disaster of deaths from the beginning of humanity at the present time. In this research paper our focus is to make a Disaster Resistance Structure having the solution of dense populated urban cities area by high vertical expansion HYBRID STRUCTURE. Our efforts are to analyse the Reinforced Concrete Hybrid Structure at different seismic zones, these concrete frames were analyzed using the response spectrum method to calculate and compare the different seismic displacement and drift. Seismic analysis by this method generally is based on dynamic analysis of building. Analysis results shows that the Reinforced Concrete Building at seismic Zone V having maximum peak story shear, base shear, drift and node displacement as compare to the analytical results of Reinforced Concrete Building at seismic Zone III and Zone IV. This analysis results indicating to focus on structural drawings strictly at construction site to make a HYBRID STRUCTURE. The study case is deal with the 10 story height of a vertical expansion Hybrid frame structure at different zones i.e. zone III, zone IV and zone V having the column 0.45x0.36mt and beam 0.6x0.36mt. with total height of 30mt, to make the structure more stable bracing techniques shell be applied like mage bracing and V shape bracing. If this kind of efforts or structure drawings are followed by the builders and contractors then we save the lives during earthquake disaster at Bhuj (Gujarat State, India) on 26th January, 2001 which resulted in more than 19,000 deaths. This kind of Disaster Resistance Structure having the capabilities to solve the problems of densely populated area of cities by the utilization of area in vertical expansion hybrid structure. We request to Government of India to make new plans and implementing it to save the lives from future disasters instead of unnecessary wants of development plans like Bullet Trains.

Keywords: history, irresponsibilities, unplanned social structure, humanity, hybrid structure, response spectrum analysis, DRIFT, and NODE displacement

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33 Vibration Based Structural Health Monitoring of Connections in Offshore Wind Turbines

Authors: Cristobal García

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The visual inspection of bolted joints in wind turbines is dangerous, expensive, and impractical due to the non-possibility to access the platform by workboat in certain sea state conditions, as well as the high costs derived from the transportation of maintenance technicians to offshore platforms located far away from the coast, especially if helicopters are involved. Consequently, the wind turbine operators have the need for simpler and less demanding techniques for the analysis of the bolts tightening. Vibration-based structural health monitoring is one of the oldest and most widely-used means for monitoring the health of onshore and offshore wind turbines. The core of this work is to find out if the modal parameters can be efficiently used as a key performance indicator (KPIs) for the assessment of joint bolts in a 1:50 scale tower of a floating offshore wind turbine (12 MW). A non-destructive vibration test is used to extract the vibration signals of the towers with different damage statuses. The procedure can be summarized in three consecutive steps. First, an artificial excitation is introduced by means of a commercial shaker mounted on the top of the tower. Second, the vibration signals of the towers are recorded for 8 s at a sampling rate of 20 kHz using an array of commercial accelerometers (Endevco, 44A16-1032). Third, the natural frequencies, damping, and overall vibration mode shapes are calculated using the software Siemens LMS 16A. Experiments show that the natural frequencies, damping, and mode shapes of the tower are directly dependent on the fixing conditions of the towers, and therefore, the variations of both parameters are a good indicator for the estimation of the static axial force acting in the bolt. Thus, this vibration-based structural method proposed can be potentially used as a diagnostic tool to evaluate the tightening torques of the bolted joints with the advantages of being an economical, straightforward, and multidisciplinary approach that can be applied for different typologies of connections by operation and maintenance technicians. In conclusion, TSI, in collaboration with the consortium of the FIBREGY project, is conducting innovative research where vibrations are utilized for the estimation of the tightening torque of a 1:50 scale steel-based tower prototype. The findings of this research carried out in the context of FIBREGY possess multiple implications for the assessment of the bolted joint integrity in multiple types of connections such as tower-to-nacelle, modular, tower-to-column, tube-to-tube, etc. This research is contextualized in the framework of the FIBREGY project. The EU-funded FIBREGY project (H2020, grant number 952966) will evaluate the feasibility of the design and construction of a new generation of marine renewable energy platforms using lightweight FRP materials in certain structural elements (e.g., tower, floating platform). The FIBREGY consortium is composed of 11 partners specialized in the offshore renewable energy sector and funded partially by the H2020 program of the European Commission with an overall budget of 8 million Euros.

Keywords: SHM, vibrations, connections, floating offshore platform

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