Search results for: Lebanese virgin olive oils

Authors: Farah Diab, Mohamad Khalil, Francesca Storace, Francesca Baldini, Piero Portincasaa, Giulio Lupidi, Laura Vergani

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Thymbra spicata is a thyme-like plant belonging to the Lamiaceae family that shows a global distribution, especially in the eastern Mediterranean region. Leaves of T. spicata contain large amounts of phenols such as phenolic acids (rosmarinic acid), phenolic monoterpenes (carvacrol), and flavonoids. In Lebanon, T. spicata is currently used as a culinary herb in salad and infusion, as well as for traditional medicinal purposes. Carvacrol (5-isopropyl-2-methyl phenol), the most abundant polyphenol in the organic extract and essential oils, has a great array of pharmacological properties. In fact, carvacrol is largely employed as a food additive and neutraceutical agent. Our aim is to investigate the beneficial effects of T. spicata ethanolic extract (TE) and its main component, carvacrol, using in vitro models of hepatic steatosis and endothelial dysfunction. As a further point, we focused on investigating if and how the binding of carvacrol to albumin, the physiological transporter for drugs in the blood, might be altered by the presence of high levels of fatty acids (FAs), thus impairing the carvacrol bio-distribution in vivo. For that reason, hepatic FaO cells treated with exogenous FAs such as oleate and palmitate mimic hepatosteatosis; endothelial HECV cells exposed to hydrogen peroxide are a model of endothelial dysfunction. In these models, we measured lipid accumulation, free radical production, lipoperoxidation, and nitric oxide release before and after treatment with carvacrol. The carvacrol binding to albumin with/without high levels of long-chain FAs was assessed by absorption and emission spectroscopies. Our findings show that both TE and carvacrol (i) counteracted lipid accumulation in hepatocytes by decreasing the intracellular and extracellular lipid contents in steatotic FaO cells; (ii) decreased oxidative stress in endothelial cells by significantly reducing lipoperoxidation and free radical production, as well as, attenuating the nitric oxide release; (ii) high levels of circulating FAs reduced the binding of carvacrol to albumin. The beneficial effects of TE and carvacrol on both hepatic and endothelial cells point to a nutraceutical potential. However, high levels of circulating FAs, such as those occurring in metabolic disorders, might hinder the carvacrol transport, bio-distribution, and pharmacodynamics.

Keywords: carvacrol, endothelial dysfunction, fatty acids, non-alcoholic fatty liver diseases, serum albumin

Procedia PDF Downloads 194

Authors: Malahat Rezaee, Mahiran Basri, Raja Noor Zaliha Raja Abdul Rahman, Abu Bakar Salleh

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Sodium diclofenac is one of the most commonly used drugs of nonsteroidal anti-inflammatory drugs (NSAIDs). It is especially effective in the controlling the severe conditions of inflammation and pain, musculoskeletal disorders, arthritis, and dysmenorrhea. Formulation as nanoemulsions is one of the nanoscience approaches that have been progressively considered in pharmaceutical science for transdermal delivery of drug. Nanoemulsions are a type of emulsion with particle sizes ranging from 20 nm to 200 nm. An emulsion is formed by the dispersion of one liquid, usually the oil phase in another immiscible liquid, water phase that is stabilized using surfactant. Palm kernel oil esters (PKOEs), in comparison to other oils; contain higher amounts of shorter chain esters, which suitable to be applied in micro and nanoemulsion systems as a carrier for actives, with excellent wetting behavior without the oily feeling. This research was aimed to study the effect of O/S ratio on stability and rheological behavior of sodium diclofenac loaded and unloaded palm kernel oil esters nanoemulsion systems. The effect of different O/S ratio of 0.25, 0.50, 0.75, 1.00 and 1.25 on stability of the drug-loaded and unloaded nanoemulsion formulations was evaluated by centrifugation, freeze-thaw cycle and storage stability tests. Lecithin and cremophor EL were used as surfactant. The stability of the prepared nanoemulsion formulations was assessed based on the change in zeta potential and droplet size as a function of time. Instability mechanisms including coalescence and Ostwald ripening for the nanoemulsion system were discussed. In comparison between drug-loaded and unloaded nanoemulsion formulations, drug-loaded formulations represented smaller particle size and higher stability. In addition, the O/S ratio of 0.5 was found to be the best ratio of oil and surfactant for production of a nanoemulsion with the highest stability. The effect of O/S ratio on rheological properties of drug-loaded and unloaded nanoemulsion systems was studied by plotting the flow curves of shear stress (τ) and viscosity (η) as a function of shear rate (γ). The data were fitted to the Power Law model. The results showed that all nanoemulsion formulations exhibited non-Newtonian flow behaviour by displaying shear thinning behaviour. Viscosity and yield stress were also evaluated. The nanoemulsion formulation with the O/S ratio of 0.5 represented higher viscosity and K values. In addition, the sodium diclofenac loaded formulations had more viscosity and higher yield stress than drug-unloaded formulations.

Keywords: nanoemulsions, palm kernel oil esters, sodium diclofenac, rheoligy, stability

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Authors: Ali Zaker, Zhi Chen

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

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

Procedia PDF Downloads 179

Authors: R. A. Abdel Rahman, A. E. Abdel Wahab, E. A. Goghneimy, H. F. Mohamed, E. M. Salama

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Infectious diseases are a major cause of death worldwide. The treatment of infections continues to be problematic in modern time because of the severe side effects of some drugs and the growing resistance to antimicrobial agents. Hence, the search for newer, safer and more potent antimicrobials is a pressing need. Herbal medicines have received much attention as a source of new antibacterial drugs since they are considered time-tested and comparatively safe both for human use and the environment. In the present study, the antimicrobial activity of marjoram (Origanum majorana L.) essential oil on some gram positive and gram negative reference bacteria, as well as some hospital resistant microbes, was tested. Marjoram oil was extracted and the oil chemical constituents were identified using GC/MS analysis. Staphylococcus aureas ATCC 6923, Pseudomonus auregonosa ATCC 9027, Bacillus subtilis ATCC 6633, E. coli ATCC 8736 and two hospital resistant microbes isolates 16 and 21 were used. The two isolates were identified by biochemical tests and 16s rRNA as proteus spp. and Enterococcus facielus. The effect of different concentrations of essential oils on bacterial growth was tested using agar disk diffusion assay method to determine the minimum inhibitory concentrations and using micro dilution method to determine the minimum bactericidal concentrations. Marjoram oil was found to be effective against both reference and hospital resistance strains. Hospital strains were more resistant to marjoram oil than reference strains. P. auregonosa growth was completely inhibited at a low concentration of oil (4µl/ml). The other reference strains showed sensitivity to marjoram oil at concentrations ranged from 5 to 7µl/ml. The two hospital strains showed sensitivity at media containing 10 and 15µl/ml oil. The major components of oil were terpineol, cis-beta (23.5%), 1,6 – octadien –3-ol,3,7-dimethyl, 2 aminobenzoate (10.9%), alpha terpieol (8.6%) and linalool (6.3%). Scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis were used to determine the difference between treated and untreated hospital strains. SEM results showed that treated cells were smaller in size than control cells. TEM data showed that cell lysis has occurred to treated cells. Treated cells have ruptured cell wall and appeared empty of cytoplasm compared to control cells which shown to be intact with normal volume of cytoplasm. The results indicated that marjoram oil has a positive antimicrobial effect on hospital resistance microbes. Natural crude extracts can be perfect resources for new antimicrobial drugs.

Keywords: antimicrobial activity, essential oil, hospital resistance microbes, marjoram

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Authors: Zoltan Sebestyen, Eszter Barta-Rajnai, Emma Jakab, Zsuzsanna Czegeny

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Extraction of the energy content of lignocellulosic biomass is one of the possible pathways to reduce the greenhouse gas emission derived from the burning of the fossil fuels. The application of the bioenergy can mitigate the energy dependency of a country from the foreign natural gas and the petroleum. The diversity of the plant materials makes difficult the utilization of the raw biomass in power plants. This problem can be overcome by the application of thermochemical techniques. Pyrolysis is the thermal decomposition of the raw materials under inert atmosphere at high temperatures, which produces pyrolysis gas, biooil and charcoal. The energy content of these products can be exploited by further utilization. The differences in the chemical and physical properties of the raw biomass materials can be reduced by the use of torrefaction. Torrefaction is a promising mild thermal pretreatment method performed at temperatures between 200 and 300 °C in an inert atmosphere. The goal of the pretreatment from a chemical point of view is the removal of water and the acidic groups of hemicelluloses or the whole hemicellulose fraction with minor degradation of cellulose and lignin in the biomass. Thus, the stability of biomass against biodegradation increases, while its energy density increases. The volume of the raw materials decreases so the expenses of the transportation and the storage are reduced as well. Biooil is the major product during pyrolysis and an important by-product during torrefaction of biomass. The composition of biooil mostly depends on the quality of the raw materials and the applied temperature. In this work, thermoanalytical techniques have been used to study the qualitative and quantitative composition of the pyrolysis and torrefaction oils of a woody (black locust) and two herbaceous samples (rape straw and wheat straw). The biooil contains C5 and C6 anhydrosugar molecules, as well as aromatic compounds originating from hemicellulose, cellulose, and lignin, respectively. In this study, special emphasis was placed on the formation of the lignin monomeric products. The structure of the lignin fraction is different in the wood and in the herbaceous plants. According to the thermoanalytical studies the decomposition of lignin starts above 200 °C and ends at about 500 °C. The lignin monomers are present among the components of the torrefaction oil even at relatively low temperatures. We established that the concentration and the composition of the lignin products vary significantly with the applied temperature indicating that different decomposition mechanisms dominate at low and high temperatures. The evolutions of decomposition products as well as the thermal stability of the samples were measured by thermogravimetry/mass spectrometry (TG/MS). The differences in the structure of the lignin products of woody and herbaceous samples were characterized by the method of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). As a statistical method, principal component analysis (PCA) has been used to find correlation between the composition of lignin products of the biooil and the applied temperatures.

Keywords: pyrolysis, torrefaction, biooil, lignin

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Authors: Tsega Asresa, Getahun Tigistu, Melaku Bayih

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Computer vision is a subfield of artificial intelligence that allows computers and systems to extract meaning from digital images and video. It is used in a wide range of fields of study, including self-driving cars, video surveillance, medical diagnosis, manufacturing, law, agriculture, quality control, health care, facial recognition, and military applications. Aromatic medicinal plants are botanical raw materials used in cosmetics, medicines, health foods, essential oils, decoration, cleaning, and other natural health products for therapeutic and Aromatic culinary purposes. These plants and their products not only serve as a valuable source of income for farmers and entrepreneurs but also going to export for valuable foreign currency exchange. In Ethiopia, there is a lack of technologies for the classification and identification of Aromatic medicinal plant parts and disease type cured by aromatic medicinal plants. Farmers, industry personnel, academicians, and pharmacists find it difficult to identify plant parts and disease types cured by plants before ingredient extraction in the laboratory. Manual plant identification is a time-consuming, labor-intensive, and lengthy process. To alleviate these challenges, few studies have been conducted in the area to address these issues. One way to overcome these problems is to develop a deep learning model for efficient identification of Aromatic medicinal plant parts with their corresponding disease type. The objective of the proposed study is to identify the aromatic medicinal plant parts and their disease type classification using computer vision technology. Therefore, this research initiated a model for the classification of aromatic medicinal plant parts and their disease type by exploring computer vision technology. Morphological characteristics are still the most important tools for the identification of plants. Leaves are the most widely used parts of plants besides roots, flowers, fruits, and latex. For this study, the researcher used RGB leaf images with a size of 128x128 x3. In this study, the researchers trained five cutting-edge models: convolutional neural network, Inception V3, Residual Neural Network, Mobile Network, and Visual Geometry Group. Those models were chosen after a comprehensive review of the best-performing models. The 80/20 percentage split is used to evaluate the model, and classification metrics are used to compare models. The pre-trained Inception V3 model outperforms well, with training and validation accuracy of 99.8% and 98.7%, respectively.

Keywords: aromatic medicinal plant, computer vision, convolutional neural network, deep learning, plant classification, residual neural network

Procedia PDF Downloads 192

Authors: Anushka Saxena, Rakhi Wahee Pratap

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Skincare textiles, an emerging field at the crossroads of textile technology and wellness, offer groundbreaking innovations that aim to enhance health and well-being through everyday wear. This research paper explores the diverse spectrum of skin-friendly textiles, with a focus on key categories such as cosmetotextiles, skincare finishes, marine collagen fabrics, and nanotextiles. These developments reflect a shift towards a more holistic approach to clothing, where garments not only serve as fashion or protection but also contribute actively to personal care and wellness. Cosmetotextiles represent a transformative fusion of beauty and textile industries, where fabrics are impregnated with active cosmetic ingredients that provide skincare benefits as they are worn. By incorporating substances such as vitamins, moisturizers, essential oils, and antioxidants, these textiles continuously release beneficial ingredients to the skin throughout the day. The result is improved skin hydration, enhanced smoothness, and targeted therapeutic effects that redefine how clothing can interact with the body. Marine collagen fabrics introduce a novel approach to skincare, harnessing collagen derived from marine life to improve skin elasticity, hydration, and overall texture. With their natural bioactive compounds, these textiles can help stimulate skin repair and rejuvenation, positioning them as a promising tool in both beauty and medical applications. Marine collagen offers the dual benefit of contributing to sustainable textiles while delivering scientifically-backed skincare benefits. Nanotextiles, on the other hand, leverage the advancements in nanotechnology by integrating nanoparticles into fabric structures. These textiles exhibit multifunctional properties, such as antimicrobial action, UV protection, and wound-healing capabilities, making them highly suitable for medical textiles. Nanotextiles provide an avenue for creating clothing that not only protects the skin from environmental aggressors but also aids in recovery, regeneration, and long-term health maintenance. This paper provides an in-depth overview of healing textiles, examining their current advancements, practical applications, and the challenges faced in their development. Furthermore, it explores the future prospects of this innovative field, particularly its potential in bridging the gap between cutting-edge technology and traditional textile practices. As consumer demand for multifunctional and health-promoting textiles grows, healing textiles present a promising solution for improving quality of life through fabric innovation.

Keywords: skincare textiles, nanotechnology, cosmetotextiles, nanotextiles, marine collagen textiles and health

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

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

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

Procedia PDF Downloads 126

Authors: Sidharth Talan, Sanjay Kumar Sharma, Eoin Joseph Wallace, Nikita Agrawal

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Underground mining is at the core of rapidly evolving metals and minerals sector due to the increasing mineral consumption globally. Even though the surface mines are still more abundant on earth, the scales of industry are slowly tipping towards underground mining due to rising depth and complexities of orebodies. Thus, the efficient and productive functioning of underground operations depends significantly on the synchronized performance of key elements such as operating site, mining equipment, manpower and mine services. Production drilling is the process of conducting long hole drilling for the purpose of charging and blasting these holes for the production of ore in underground metal mines. Thus, production drilling is the crucial segment in the underground metal mining value chain. This paper presents the process mapping tool to evaluate the production drilling process in the underground metal mining operation by dividing the given process into three segments namely Input, Process and Output. The three segments are further segregated into factors and sub-factors. As per the study, the major input factors crucial for the efficient functioning of production drilling process are power, drilling water, geotechnical support of the drilling site, skilled drilling operators, services installation crew, oils and drill accessories for drilling machine, survey markings at drill site, proper housekeeping, regular maintenance of drill machine, suitable transportation for reaching the drilling site and finally proper ventilation. The major outputs for the production drilling process are ore, waste as a result of dilution, timely reporting and investigation of unsafe practices, optimized process time and finally well fragmented blasted material within specifications set by the mining company. The paper also exhibits the drilling loss matrix, which is utilized to appraise the loss in planned production meters per day in a mine on account of availability loss in the machine due to breakdowns, underutilization of the machine and productivity loss in the machine measured in drilling meters per unit of percussion hour with respect to its planned productivity for the day. The given three losses would be essential to detect the bottlenecks in the process map of production drilling operation so as to instigate the action plan to suppress or prevent the causes leading to the operational performance deficiency. The given tool is beneficial to mine management to focus on the critical factors negatively impacting the production drilling operation and design necessary operational and maintenance strategies to mitigate them. 

Keywords: process map, drilling loss matrix, SIPOC, productivity, percussion rate

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Authors: Abeer Al Kalbani

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Oman is a sub-tropical country with limited water resources, harsh weather and limited soil fertility, constraining food production. Therefore, it largely depends on international markets to assure supply of food. In the light of these circumstances, food security in Oman is defined as the ability of the country to grant the staple food needs of people (e.g. rice, wheat, lentil, sugar, dates, dairy products, fish and plant or vegetable oils). It also involves exporting local goods with high production rates to exchange them with required food products. This concept of food security includes the availability of food through production and/or importing, stability of the market prices during all circumstances, and the ability of people to meet their needs within their income capabilities. As a result, most of the food security work is focused on availability and access dimensions of the issue. Not much research is focused on the utilization aspect of food security in Oman. Although women play a vital role in food security, there is limited research on women’s role in food security neither in Oman nor in neighboring Gulf countries. Women play an important role not only by carrying the responsibility of feeding their families but also by setting the consumption model for the household. Therefore, the research aims to contribute to the work done on food security in Oman and similar regions of the world by studying the role women play at the utilization level. Methods used in this research include Qualitative unstructured interviews, focus groups, survey questionnaire and an experimental study. Based on the FAO definition of food security, it consists of availability, access, utilization and sustainability. Results from a pilot study conducted for this research on two groups of women in Oman; urban and rural women, showed that women in Oman are responsible for achieving these four pillars at the household level. Moreover, awareness of women increased as their educational level increased. Urban women showed more awareness and openness to adopt healthier and proper food related choices than rural women. Urban women seem also more open than rural women to new ideas and concepts and ways to healthier food. However, both urban and rural women claim that no training and educational programs are available for them and awareness of food security in general remains relatively low in both groups. In the light of these findings, this research attempts to further investigate the social beliefs, practices and attitudes women adopt in relation to food purchase, storage, preparation and consumption as considered as important parts of the food system. It also seeks to examine the effect of educational training programs and media on the level of women awareness on the issue.

Keywords: food security, household food security, utilization, role of women

Procedia PDF Downloads 407

Authors: Gómez S. Jennifer, Méndez V. Camila, Moncayo M. Diana, Vega M. Lizeth

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The cape gooseberry is a climacteric fruit; Colombia is one of the principal exporters in the world. The environmental condition of temperature and relative moisture decreases the titratable acidity and pH. These conditions and fruit maturation result in the fungal proliferation of Botrytis cinerea disease. Plastic packaging for fresh cape gooseberries was used for mechanical damage protection but created a suitable atmosphere for fungal growth. Beta-cyclodextrins are currently implemented as coatings for the encapsulation of hydrophobic compounds, for example, with bioactive compounds from essential oils such as cinnamaldehyde, which has a high antimicrobial capacity. However, it is a volatile substance. In this article, the casting method was used to obtain a polylactic acid (PLA) polymer film containing the beta-cyclodextrin-cinnamaldehyde inclusion complex, generating an insert that allowed the controlled release of the antifungal substance in packed cape gooseberries to decrease contamination by Botrytis cinerea in a latent state during storage. For the encapsulation technique, three ratios for the cinnamaldehyde: beta-cyclodextrin inclusion complex were proposed: (25:75), (40:60), and (50:50). Spectrophotometry, colorimetry in L*a*b* coordinate space and scanning electron microscopy (SEM) were made for the complex characterization. Subsequently, two ratios of tween and water (40:60) and (50:50) were used to obtain the polylactic acid (PLA) film. To determine mechanical and physical parameters of colourimetry in L*a*b* coordinate space, atomic force microscopy and stereoscopy were done to determine the transparency and flexibility of the film; for both cases, Statgraphics software was used to determine the best ratio in each of the proposed phases, where for encapsulation it was (50:50) with an encapsulation efficiency of 65,92%, and for casting the ratio (40:60) obtained greater transparency and flexibility that permitted its incorporation into the polymeric packaging. A liberation assay was also developed under ambient temperature conditions to evaluate the concentration of cinnamaldehyde inside the packaging through gas chromatography for three weeks. It was found that the insert had a controlled release. Nevertheless, a higher cinnamaldehyde concentration is needed to obtain the minimum inhibitory concentration for the fungus Botrytis cinerea (0.2g/L). The homogeneity of the cinnamaldehyde gas phase inside the packaging can be improved by considering other insert configurations. This development aims to impact emerging food preservation technologies with the controlled release of antifungals to reduce the affectation of the physico-chemical and sensory properties of the fruit as a result of contamination by microorganisms in the postharvest stage.

Keywords: antifungal, casting, encapsulation, postharvest

Procedia PDF Downloads 75

Authors: Stephanie PB Caligiuri, Harold M Aukema, Delfin Rodriguez-Leyva, Amir Ravandi, Randy Guzman, Grant N. Pierce

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Background: Hypertension leads to cardiac and cerebral events and therefore is the leading risk factor attributed to death in the world. Oxylipins may be mediators in these events as they can regulate vascular tone and inflammation. Oxylipins are derived from fatty acids. Dietary flaxseed is rich in the n3 fatty acid, alpha-linolenic acid, and, therefore, may have the ability to change the substrate profile of oxylipins. As a result, this could alter blood pressure. Methods: A randomized, double-blinded, controlled clinical trial, the Flax-PAD trial, was used to assess the impact of dietary flaxseed on blood pressure (BP), and to also assess the relationship of plasma oxylipins to BP in 81 patients with peripheral arterial disease (PAD). Patients with PAD were chosen for the clinical trial as they are at an increased risk for hypertension and cardiac and cerebral events. Thirty grams of ground flaxseed were added to food products to consume on a daily basis for 6 months. The control food products contained wheat germ, wheat bran, and mixed dietary oils instead of flaxseed. Central BP, which is more significantly associated to organ damage, cardiac, and cerebral events versus brachial BP, was measured by pulse wave analysis at baseline and 6 months. A plasma profile of 43 oxylipins was generated using solid phase extraction, HPLC-MS/MS, and stable isotope dilution quantitation. Results: At baseline, the central BP (systolic/diastolic) in the placebo and flaxseed group were, 131/73 ± 2.5/1.4 mmHg and 128/71 ± 2.6/1.4 mmHg, respectively. After 6 months of intervention, the flaxseed group exhibited a decrease in blood pressure of 4.0/1.0 mmHg. The 6 month central BP in the placebo and flaxseed groups were, 132/74 ± 2.9/1.8 mmHg and 124/70 ± 2.6/1.6 mmHg (P<0.05). Correlation and logistic regression analyses between central blood pressure and oxylipins were performed. Significant associations were observed between central blood pressure and 17 oxylipins, primarily produced from arachidonic acid. Every 1 nM increase in 16-hydroxyeicosatetraenoic acid (HETE) increased the odds of having high central systolic BP by 15-fold, of having high central diastolic BP by 6-fold and of having high central mean arterial pressure by 15-fold. In addition, every 1 nM increase in 5,6-dihydroxyeicosatrienoic acid (DHET) and 11,12-DHET increased the odds of having high central mean arterial pressure by 45- and 18-fold, respectively. Flaxseed induced a significant decrease in these as well as 4 other vasoconstrictive oxylipins. Conclusion: Dietary flaxseed significantly lowered blood pressure in patients with PAD and hypertension. Plasma oxylipins were strongly associated with central blood pressure and may have mediated the flaxseed-induced decrease in blood pressure.

Keywords: hypertension, flaxseed, oxylipins, peripheral arterial disease

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Authors: Galina N. Parshina, Olga N. Shemshura, Ulzhan S. Mukiyanova, Gulnur M. Beisetbayeva

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From a medical point of view some species from the family Lamiaceae Lindl. attract the attention of scientists. Many plant species from this family are used in science and medicine. Some researchers believe that the medicinal properties of these plants are caused by the action on the organism of the individual components (camphor, menthol, thymol, eugenol, phenols, flavonoids, alcohols, and their derivatives) or the entire complex of essential oils. Biologically active substances (BAS), isolated from these medicinal plants can be an effective supplement in the complex treatment of infectious diseases. The substances of the phenolic group such as flavonoids and phenolic acids; and also alkaloids included in the component composition of the plants from the family Lamiaceae Lindl. present the scientific and practical interest for future investigations of their biological activity and development of medicinal products. The research objects are the species from the family Lamiaceae Lindl., cultivated in the North-Kazakhstan region. In this abstract, we present the results of the investigation of polyphenolic complex (flavonoids and phenolic acids) and alkaloids in aqueous and ethanol extracts. Investigation of the qualitative composition of flavonoids in the aqueous extracts showed that the species Monarda Diana contains flavone, Dracocephalum moldavica contains rutin, Ocimum basilicum (purple form) contains both ruin and quercetin. Biochemical analysis revealed that the ethanol extract of Monarda Diana has phenolic acids, similar to protocatechuic and benzoic acids by their chromatographic characteristics. But the aqueous extract contains four phenolic acids, one of which is an analogue of gentisic acid; and the other three are not identified yet. The phenolic acids such as benzoic and gentisic acids identified in ethanol extracts of species Ocimum basilicum (purple form) and Satureja hortensis, correspondingly. But the same phenolic acids did not appear in aqueous extracts. The phenolic acids were not determined neither in the ethanol or aqueous extracts of species Dracocephalum moldavica. The biochemical analysis did not reveal the content of alkaloids in aqueous extracts of investigated plants. However, the alkaloids in the amount of 5-13 components were identified in the ethanolic extracts of plants by the qualitative reactions. The results of analysis with reagent of Dragendorff showed that next amounts of alkaloids were identified in extracts of Monarda Diana (6-7), Satureja hortensis (6), Ocimum basilicum (7-9) and Dracocephalum moldavica (5-6). The reactions with reagent of Van-Urca showed that next amounts of alkaloids were identified in extracts of Monarda Diana (9-12), Satureja hortensis (9-10), two alkaloids of them with Rf6=0,39 and Rf6=0,31 similar to roquefortine), Ocimum basilicum (11) and Dracocephalum moldavica (13, two of them with Rf5=0,34 and Rf5=0,33 by their chromatographic characteristics similar to epikostaklavin).

Keywords: biologically active substances, Lamiaceae, component composition, medicinal plant

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Authors: Sherif Fakher

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Hydrogen has been gaining a lot of global attention as an uprising contributor in the energy sector. Labeled as an energy carrier, hydrogen is used in many industries and can be used to generate electricity via fuel cells. Blue hydrogen involves the production of hydrogen from hydrocarbons using different processes that emit CO₂. However, the CO₂ is captured and stored. Hence, very little environmental damage occurs during the hydrogen production process. This research investigates the ability to use different catalysts for the production of hydrogen from different hydrocarbon sources, including coal, oil, and gas, using a two-step Aquathermolysis reaction. The research presents the results of experiments conducted to evaluate different catalysts and also highlights the main advantages of this process over other blue hydrogen production methods, including methane steam reforming, autothermal reforming, and oxidation. Two methods of hydrogen generation were investigated including partial oxidation and aquathermolysis. For those two reactions, the reaction kinetics, thermodynamics, and medium were all investigated. Following this, experiments were conducted to test the hydrogen generation potential from both methods. The porous media tested were sandstone, ash, and prozzolanic material. The spent oils used were spent motor oil and spent vegetable oil from cooking. Experiments were conducted at temperatures up to 250 C and pressures up to 3000 psi. Based on the experimental results, mathematical models were developed to predict the hydrogen generation potential at higher thermodynamic conditions. Since both partial oxidation and aquathermolysis require relatively high temperatures to undergo, it was important to devise a method by which these high temperatures can be generated at a low cost. This was done by investigating two factors, including the porous media used and the reliance on the spent oil. Of all the porous media used, the ash had the highest thermal conductivity. The second step was the partial combustion of part of the spent oil to generate the heat needed to reach the high temperatures. This reduced the cost of the heat generation significantly. For the partial oxidation reaction, the spent oil was burned in the presence of a limited oxygen concentration to generate carbon monoxide. The main drawback of this process was the need for burning. This resulted in the generation of other harmful and environmentally damaging gases. Aquathermolysis does not rely on burning, which makes it the cleaner alternative. However, it needs much higher temperatures to run the reaction. When comparing the hydrogen generation potential for both using gas chromatography, aquathermolysis generated 23% more hydrogen using the same volume of spent oil compared to partial oxidation. This research introduces the concept of using spent oil for hydrogen production. This can be a very promising method to produce a clean source of energy using a waste product. This can also help reduce the reliance on freshwater for hydrogen generation which can divert the usage of freshwater to other more important applications.

Keywords: blue hydrogen production, catalytic aquathermolysis, direct carbon dioxide capture, CCUS

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Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Ching Shya Lee, Mohamed Kheireddine Aroua, Wan Mohd Ashri Wan Daud, Patrick Cognet, Yolande Peres, Mohammed Ajeel

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In recent years, with the decreasing supply of fossil fuel, renewable energy has received a significant demand. Biodiesel which is well known as vegetable oil based fatty acid methyl ester is an alternative fuel for diesel. It can be produced from transesterification of vegetable oils, such as palm oil, sunflower oil, rapeseed oil, etc., with methanol. During the transesterification process, crude glycerol is formed as a by-product, resulting in 10% wt of the total biodiesel production. To date, due to the fast growing of biodiesel production in worldwide, the crude glycerol supply has also increased rapidly and resulted in a significant price drop for glycerol. Therefore, extensive research has been developed to use glycerol as feedstock to produce various added-value chemicals, such as tartronic acid, mesoxalic acid, glycolic acid, glyceric acid, propanediol, acrolein etc. The industrial processes that usually involved are selective oxidation, biofermentation, esterification, and hydrolysis. However, the conversion of glycerol into added-value compounds by electrochemical approach is rarely discussed. Currently, the approach is mainly focused on the electro-oxidation study of glycerol under potentiostatic mode for cogenerating energy with other chemicals. The electro-organic synthesis study from glycerol under galvanostatic mode is seldom reviewed. In this study, the glycerol was converted into various added-value compounds by electrochemical method under galvanostatic mode. This work aimed to study the possible compounds produced from glycerol by electrochemical technique in a one-pot electrolysis cell. The electro-organic synthesis study from glycerol was carried out in a single compartment reactor for 8 hours, over the platinum cathode and anode electrodes under acidic condition. Various parameters such as electric current (1.0 A to 3.0 A) and reaction temperature (27 °C to 80 °C) were evaluated. The products obtained were characterized by using gas chromatography-mass spectroscopy equipped with an aqueous-stable polyethylene glycol stationary phase column. Under the optimized reaction condition, the glycerol conversion achieved as high as 95%. The glycerol was successfully converted into various added-value chemicals such as ethylene glycol, glycolic acid, glyceric acid, acetaldehyde, formic acid, and glyceraldehyde; given the yield of 1%, 45%, 27%, 4%, 0.7% and 5%, respectively. Based on the products obtained from this study, the reaction mechanism of this process is proposed. In conclusion, this study has successfully converted glycerol into a wide variety of added-value compounds. These chemicals are found to have high market value; they can be used in the pharmaceutical, food and cosmetic industries. This study effectively opens a new approach for the electrochemical conversion of glycerol. For further enhancement on the product selectivity, electrode material is an important parameter to be considered.

Keywords: biodiesel, glycerol, electrochemical conversion, galvanostatic mode

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

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

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

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Authors: H. Arceo, S. Rincon, C. Ben-Youssef, J. Rivera, A. Zepeda

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Biodiesel has emerged as a material with great potential as a renewable energy replacement to current petroleum-based diesel. Recently, biodiesel production is focused on the development of more efficient, sustainable process with lower costs of production. In this sense, a “green” approach to biodiesel production has stimulated the use of sustainable heterogeneous acid catalysts, that are better alternatives to conventional processes because of their simplicity and the simultaneous promotion of esterification and transesterification reactions from low-grade, highly-acidic and water containing oils without the formation of soap. The focus of this methodology is the development of new heterogeneous catalysts that under ordinary reaction conditions could reach yields similar to homogeneous catalysis. In recent years, metal organic frameworks (MOF) have attracted much interest for their potential as heterogeneous acid catalysts. They are crystalline porous solids formed by association of transition metal ions or metal–oxo clusters and polydentate organic ligands. This hybridization confers MOFs unique features such as high thermal stability, larger pore size, high specific area, high selectivity and recycling potential. Thus, MOF application could be a way to improve the biodiesel production processes. In this work, we evaluated the catalytic activity of MOF [(4,4-bipyridine)2(O₂CCH₃)2Zn]n (MOF Zn-I) for the synthesis of biodiesel from canola oil. The reaction conditions were optimized using the response surface methodology with a compound design central with 24. The variables studied were: Reaction temperature, amount of catalyst, molar ratio oil: MetOH and reaction time. The preparation MOF Zn-I was performed by mixing 5 mmol 4´4 dipyridine dissolved in 25 mL methanol with 10 mmol Zn(O₂CCH₃)₂ ∙ 2H₂O in 25 mL water. The crystals were obtained by slow evaporation of the solvents at 60°C for 18 h. The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). Experiments were performed using commercially available canola oil in ace pressure tube under continuous stirring. The reaction was filtered and vacuum distilled to remove the catalyst and excess alcohol, after which it was centrifuged to separate the obtained biodiesel and glycerol. 1H NMR was used to calculate the process yield. GC-MS was used to quantify the fatty acid methyl ester (FAME). The results of this study show that the acid catalyst MOF Zn-I could be used as catalyst for biodiesel production through heterogeneous transesterification of canola oil with FAME yield 82 %. The optimum operating condition for the catalytic reaction were of 142°C, 0.5% catalyst/oil weight ratio, 1:30 oil:MeOH molar ratio and 5 h reaction time.

Keywords: fatty acid methyl ester, heterogeneous acid catalyst, metal organic framework, transesterification

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Authors: Ana Maria Muț, Georgeta Coneac, Ioana Olariu, Ștefana Avram, Ioana Zinuca Pavel, Ionela Daliana Minda, Lavinia Vlaia, Cristina Adriana Dehelean, Corina Danciu

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Oregano essential oil is obtained from different parts of the plant Origanum vulgare (fam. Lamiaceae) and carvacrol and thymol are primary components, widely recognized for their antimicrobial activity, as well as their antiviral and antifungal properties. Poloxamers are triblock copolymers (Pluronic®), formed of three non-ionic blocks with a hydrophobic polyoxypropylene central chain flanked by two polyoxyethylene hydrophilic chains. They are known for their biocompatibility, sensitivity to temperature changes (sol-to-gel transition of aqueous solution with temperature increase), but also for their amphiphilic and surface active nature determining the formation of micelles, useful for solubilization of different hydrophobic compounds such as the terpenes and terpenoids contained in essential oils. Thus, these polymers, listed in European and US Pharmacopoeia and approved by FDA, are widely used as solubilizers and gelling agents for various pharmaceutical preparations, including topical hydrogels. The aim of this study was to investigate the posibility of solubilizing oregano essential oil (OEO) in polymeric micelles using polyoxypropylene (PPO)-polyoxyethylene (PEO)-polyoxypropylene (PPO) triblock polymers to obtain semisolid systems suitable for topical application. A formulation screening was performed, using Pluronic® F-127 in concentration of 20%, Pluronic® L-31, Pluronic® L-61 and Pluronic® L-62 in concentration of 0.5%, 0.8% respectively 1% to obtain the polymeric micelles-based systems. Then, to each selected system, with or without 10% absolute ethanol, 5% or 8% OEO was added. The obtained transparent poloxamer-based hydrogels containing solubilized OEO were further evaluated for pH, rheological characteristics (flow behaviour, viscosity, consistency and spreadability), using consacrated techniques like potentiometric titration, stationary shear flow test, penetrometric method and parallel plate method. Also, in vitro release and permeation of carvacrol from the hydrogels was carried out, using vertical diffusion cells and synthetic hydrophilic membrane and porcine skin respectively. The pH values and rheological features of all tested formulations were in accordance with official requirements for semisolid cutaneous preparations. But, the formulation containing 0.8% Pluronic® L-31, 10% absolute ethanol, 8% OEO and water and the formulation with 1% Pluronic® L-31, 5% OEO and water, produced the highest cumulative amounts of carvacrol released/permeated through the membrane. The present study demonstrated that oregano essential oil can be successfully solubilized in the investigated poloxamer-based hydrogels. These systems can be further investigated as potential topical therapy for cutaneous papillomas. Funding: This research was funded by Project PN-III-P1-1.1-TE2019-0130, Contract number TE47, Romania.

Keywords: oregano essential oil, carvacrol, poloxamer, topical hydrogels

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Authors: Anna Drabczyk, Sonia Kudlacik-Kramarczyk, Dagmara Malina, Bozena Tyliszczak, Agnieszka Sobczak-Kupiec

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Nowadays, nano-size materials are very popular group of materials among scientists. What is more, these materials find an application in a wide range of various areas. Therefore constantly increasing demand for nanomaterials including metallic nanoparticles such as silver of gold ones is observed. Therefore, new routes of their preparation are sought. Considering potential application of nanoparticles, it is important to select an adequate methodology of their preparation because it determines their size and shape. Among the most commonly applied methods of preparation of nanoparticles chemical and electrochemical techniques are leading. However, currently growing attention is directed into the biological or biochemical aspects of syntheses of metallic nanoparticles. This is associated with a trend of developing of new routes of preparation of given compounds according to the principles of green chemistry. These principles involve e.g. the reduction of the use of toxic compounds in the synthesis as well as the reduction of the energy demand or minimization of the generated waste. As a result, a growing popularity of the use of such components as natural plant extracts, infusions or essential oils is observed. Such natural substances may be used both as a reducing agent of metal ions and as a stabilizing agent of formed nanoparticles therefore they can replace synthetic compounds previously used for the reduction of metal ions or for the stabilization of obtained nanoparticles suspension. Methods that proceed in the presence of previously mentioned natural compounds are environmentally friendly and proceed without the application of any toxic reagents. Methodology: Presented research involves preparation of silver nanoparticles using selected plant extracts, e.g. artichoke extract. Extracts of natural origin were used as reducing and stabilizing agents at the same time. Furthermore, syntheses were carried out in the presence of additional polymeric stabilizing agent. Next, such features of obtained suspensions of nanoparticles as total antioxidant activity as well as content of phenolic compounds have been characterized. First of the mentioned studies involved the reaction with DPPH (2,2-Diphenyl-1-picrylhydrazyl) radical. The content of phenolic compounds was determined using Folin-Ciocalteu technique. Furthermore, an essential issue was also the determining of the stability of formed suspensions of nanoparticles. Conclusions: In the research it was demonstrated that metallic nanoparticles may be obtained using plant extracts or infusions as stabilizing or reducing agent. The methodology applied, i.e. a type of plant extract used during the synthesis, had an impact on the content of phenolic compounds as well as on the size and polydispersity of obtained nanoparticles. What is more, it is possible to prepare nano-size particles that will be characterized by properties desirable from the viewpoint of their potential application and such an effect may be achieved with the use of non-toxic reagents of natural origin. Furthermore, proposed methodology stays in line with the principles of green chemistry.

Keywords: green chemistry principles, metallic nanoparticles, plant extracts, stabilization of nanoparticles

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Authors: L. Le Priol, A. Nesterenko, K. El Kirat, K. Saleh

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Introduction and objectives: Polyunsaturated fatty acids (PUFAs) omega-3 and omega-6 are widely recognized as being beneficial to the health and normal growth. Unfortunately, due to their highly unsaturated nature, these molecules are sensitive to oxidation and thermic degradation leading to the production of toxic compounds and unpleasant flavors and smells. Hence, it is necessary to find out a suitable way to protect them. Microencapsulation by spray-drying is a low-cost encapsulation technology and most commonly used in the food industry. Many compounds can be used as wall materials, but there is a growing interest in the use of biopolymers, such as proteins and polysaccharides, over the last years. The objective of this study is to increase the oxidative stability of sunflower oil by microencapsulation in plant protein matrices using spray-drying technique. Material and methods: Sunflower oil was used as a model substance for oxidable food oils. Proteins from brown rice, hemp, pea, soy and sunflower seeds were used as emulsifiers and microencapsulation wall materials. First, the proteins were solubilized in distilled water. Then, the emulsions were pre-homogenized using a high-speed homogenizer (Ultra-Turrax) and stabilized by using a high-pressure homogenizer (HHP). Drying of the emulsion was performed in a Mini Spray Dryer. The oxidative stability of the encapsulated oil was determined by performing accelerated oxidation tests with a Rancimat. The size of the microparticles was measured using a laser diffraction analyzer. The morphology of the spray-dried microparticles was acquired using environmental scanning microscopy. Results: Pure sunflower oil was used as a reference material. Its induction time was 9.5 ± 0.1 h. The microencapsulation of sunflower oil in pea and soy protein matrices significantly improved its oxidative stability with induction times of 21.3 ± 0.4 h and 12.5 ± 0.4 h respectively. The encapsulation with hemp proteins did not significantly change the oxidative stability of the encapsulated oil. Sunflower and brown rice proteins were ineffective materials for this application, with induction times of 7.2 ± 0.2 h and 7.0 ± 0.1 h respectively. The volume mean diameter of the microparticles formulated with soy and pea proteins were 8.9 ± 0.1 µm and 16.3 ± 1.2 µm respectively. The values for hemp, sunflower and brown rice proteins could not be obtained due to the agglomeration of the microparticles. ESEM images showed smooth and round microparticles with soy and pea proteins. The surfaces of the microparticles obtained with sunflower and hemp proteins were porous. The surface was rough when brown rice proteins were used as the encapsulating agent. Conclusion: Soy and pea proteins appeared to be efficient wall materials for the microencapsulation of sunflower oil by spray drying. These results were partly explained by the higher solubility of soy and pea proteins in water compared to hemp, sunflower, and brown rice proteins. Acknowledgment: This work has been performed, in partnership with the SAS PIVERT, within the frame of the French Institute for the Energy Transition (Institut pour la Transition Energétique (ITE)) P.I.V.E.R.T. (www.institut-pivert.com) selected as an Investments for the Future (Investissements d’Avenir). This work was supported, as part of the Investments for the Future, by the French Government under the reference ANR-001-01.

Keywords: biopolymer, edible oil, microencapsulation, oxidative stability, release, spray-drying

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Authors: Zhaoyang Liu, Detao Qin, Darren Delai Sun

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The onshore production of oil and gas (for example, shale gas) generates large quantities of wastewater, referred to be ‘produced water’, which contains high contents of oils and salts. The direct discharge of produced water, if not appropriately treated, can be toxic to the environment and human health. Membrane filtration has been deemed as an environmental-friendly and cost-effective technology for treating oily wastewater. However, conventional polymeric membranes have their drawbacks of either low salt rejection rate or high membrane fouling tendency when treating oily wastewater. Recent years, forward osmosis (FO) membrane filtration has emerged as a promising technology with its unique advantages of low operation pressure and less membrane fouling tendency. However, until now there is still no report about FO membranes specially designed and fabricated for treating the oily and salty produced water. In this study, a novel nanocomposite FO membrane was developed specially for treating oil- and salt-polluted produced water. By leveraging the recent advance of nanomaterials and nanotechnology, this nanocomposite FO membrane was designed to be made of double layers: an underwater oleophobic selective layer on top of a nanomaterial infused polymeric support layer. Wherein, graphene oxide (GO) nanosheets were selected to add into the polymeric support layer because adding GO nanosheets can optimize the pore structures of the support layer, thus potentially leading to high water flux for FO membranes. In addition, polyvinyl alcohol (PVA) hydrogel was selected as the selective layer because hydrated and chemically-crosslinked PVA hydrogel is capable of simultaneously rejecting oil and salt. After nanocomposite FO membranes were fabricated, the membrane structures were systematically characterized with the instruments of TEM, FESEM, XRD, ATR-FTIR, surface zeta-potential and Contact angles (CA). The membrane performances for treating produced waters were tested with the instruments of TOC, COD and Ion chromatography. The working mechanism of this new membrane was also analyzed. Very promising experimental results have been obtained. The incorporation of GO nanosheets can reduce internal concentration polarization (ICP) effect in the polymeric support layer. The structural parameter (S value) of the new FO membrane is reduced by 23% from 265 ± 31 μm to 205 ± 23 μm. The membrane tortuosity (τ value) is decreased by 20% from 2.55 ± 0.19 to 2.02 ± 0.13 μm, which contributes to the decrease of S value. Moreover, the highly-hydrophilic and chemically-cross-linked hydrogel selective layer present high antifouling property under saline oil/water emulsions. Compared with commercial FO membrane, this new FO membrane possesses three times higher water flux, higher removal efficiencies for oil (>99.9%) and salts (>99.7% for multivalent ions), and significantly lower membrane fouling tendency (<10%). To our knowledge, this is the first report of a nanocomposite FO membrane with the combined merits of high salt rejection, high oil repellency and high water flux for treating onshore oil/gas produced waters. Due to its outstanding performance and ease of fabrication, this novel nanocomposite FO membrane possesses great application potential in wastewater treatment industry.

Keywords: nanocomposite, membrane, polymer, graphene oxide

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Authors: Rawan Ashraf, Ahmed E. Gomaa, Gehan Safwat, Ayman Diab

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Background: Three-dimensional (3D) bio-printing has become a versatile and powerful method for generating a variety of biological constructs, including bone or extracellular matrix scaffolds endo- or epithelial, muscle tissue, as well as organoids. Aim of the study: Fabricate a low cost DIY 3D bio-printer to produce 3D bio-printed products such as anti-microbial packaging or multi-organs on chips. We demonstrate the alignment between two types of 3D printer technology (3D Bio-printer and DLP) on Multi-organ-on-a-chip (multi-OoC) devices fabrication. Methods: First, Design and Fabrication of the Syringe Unit for Modification of an Off-the-Shelf 3D Printer, then Preparation of Hydrogel based on natural polymers Sodium Alginate and Gelatin, followed by acquisition of the cell suspension, then modeling the desired 3D structure. Preparation for 3D printing, then Cell-free and cell-laden hydrogels went through the printing process at room temperature under sterile conditions and finally post printing curing process and studying the printed structure regards physical and chemical characteristics. The hard scaffold of the Organ on chip devices was designed and fabricated using the DLP-3D printer, following similar approaches as the Microfluidics system fabrication. Results: The fabricated Bio-Ink was based onHydrogel polymer mix of sodium alginate and gelatin 15% to 0.5%, respectively. Later the 3D printing process was conducted using a higher percentage of alginate-based hydrogels because of it viscosity and the controllable crosslinking, unlike the thermal crosslinking of Gelatin. The hydrogels were colored to simulate the representation of two types of cells. The adaption of the hard scaffold, whether for the Microfluidics system or the hard-tissues, has been acquired by the DLP 3D printers with fabricated natural bioactive essential oils that contain antimicrobial activity, followed by printing in Situ three complex layers of soft-hydrogel as a cell-free Bio-Ink to simulate the real-life tissue engineering process. The final product was a proof of concept for a rapid 3D cell culturing approaches that uses an engineered hard scaffold along with soft-tissues, thus, several applications were offered as products of the current prototype, including the Organ-On-Chip as a successful integration between DLP and 3D bioprinter. Conclusion: Multiple designs for the organ-on-a-chip (multi-OoC) devices have been acquired in our study with main focus on the low cost fabrication of such technology and the potential to revolutionize human health research and development. We describe circumstances in which multi-organ models are useful after briefly examining the requirement for full multi-organ models with a systemic component. Following that, we took a look at the current multi-OoC platforms, such as integrated body-on-a-chip devices and modular techniques that use linked organ-specific modules.

Keywords: 3d bio-printer, hydrogel, multi-organ on chip, bio-inks

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Authors: Andrew Gray, Zhibing Zhang

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The ability for consumer products to deliver a sustained perfume response can be a key driver for a variety of applications. Many compounds in perfume oils are highly volatile, meaning they readily evaporate once the product is applied, and the longevity of the scent is poor. Perfume capsules have been introduced as a means of abating this evaporation once the product has been delivered. The impermeable capsules are aimed to be stable within the formulation, and remain intact during delivery to the desired substrate, only rupturing to release the core perfume oil through application of mechanical force applied by the consumer. This opens up the possibility of obtaining an olfactive response hours, weeks or even months after delivery, depending on the nature of the desired application. Tailoring the properties of the polymeric capsules to better address the needs of the application is not a trivial challenge and currently design of capsules is largely done by trial and error. The aim of this work is to have more predictive methods for capsule design depending on the consumer application. This means refining formulations such that they rupture at the right time for the specific consumer application, not too early, not too late. Finding the right balance between these extremes is essential if a benefit is sought with respect to neat addition of perfume to formulations. It is important to understand the forces that influence capsule rupture, first, by quantifying the magnitude of these different forces, and then by assessing bulk rupture in real-world applications to understand how capsules actually respond. Samples were provided by an industrial partner and the mechanical properties of individual capsules within the samples were characterized via a micromanipulation technique, developed by Professor Zhang at the University of Birmingham. The capsules were synthesized such as to change one particular physicochemical property at a time, such as core: wall material ratio, and the average size of capsules. Analysis of shell thickness via Transmission Electron Microscopy, size distribution via the use of a Mastersizer, as well as a variety of other techniques confirmed that only one particular physicochemical property was altered for each sample. The mechanical analysis was subsequently undertaken, showing the effect that changing certain capsule properties had on the response under compression. It was, however, important to link this fundamental mechanical response to capsule performance in real-world applications. As such, the capsule samples were introduced to a formulation and exposed to full scale stresses. GC-MS headspace analysis of the perfume oil released from broken capsules enabled quantification of what the relative strengths of capsules truly means for product performance. Correlations have been found between the mechanical strength of capsule samples and performance in terms of perfume release in consumer applications. Having a better understanding of the key parameters that drive performance benefits the design of future formulations by offering better guidelines on the parameters that can be adjusted without worrying about the performance effects, and singles out those parameters that are essential in finding the sweet spot for capsule performance.

Keywords: consumer products, mechanical and physicochemical properties, perfume capsules, rupture behaviour

Procedia PDF Downloads 131

Authors: Rebeca P Ramos-Bueno, Maria Jose Gonzalez-Fernandez, Rosa M. Moreno-Zamora, Antonia Barros Heras, Yolanda Serrano Alonso, Carolina Sanchez Barranco

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Insects are a new source of fatty acids (FA), so they are considered a sustainable and environmentally friendly alternative for both animal feed and the human diet, and furthermore, their harvesting/rearing require a low-tech and low capital investment. For that reason, lipids obtained by insect breeding open interesting possibilities with alimentary and industrial purposes, i.e., the production of biodiesel. Particularly, certain insect species, especially during the larval stage, contain high proportions of fat which is highly dependent on their feed and stage of development. Among them, Hermetia illucens larvae can be bred on food wastes to produce fat- and protein-rich raw materials for food by-product management. So, insects can act as excellent bioconverters of organic waste to nutrient-rich materials. In this regard, the aim of the study was to evaluate the effects of fruit byproducts on the FA compositions of Tenebrio molitor, Zophoba morio, and H. illucens larvae. Firstly, oil was extracted with the green solvent ethyl acetate, and FA methyl ester was obtained and analyzed by GC to show the FA profile. In addition, the triacylglycerol (TAG) profile was obtained by HPLC. Dehydrated watermelon, tomato, and papaya by-products, as well as wheat-based control feed, were assayed. High FA content was reached by Z. morio larvae fed with all fruits; however, no differences were shown in lipid profile with any change. It is worth highlighting that both Z. morio and H. illucens could be selected as the best candidates for biodiesel production due to their high content of saturated FA. On the other hand, T. molitor larvae showed a higher content of monounsaturated FA than control larvae, whereas the n-6 polyunsaturated FA content decreased in larvae fed with fruits. This result indicates that the improvement of the FA profile of Tenebrio can depend on both the type of feeding and the intended use. The lipid profile of H. illucens larvae fed with papaya and tomato showed a slight increase in the content of α-linoleic acid (ALA, 18:3n3). This FA is the precursor of docosahexaenoic acid (DHA, 22:6n3), which plays an important role as a component of structural lipids in cell membranes as well as in the synthesis of eicosanoids, protecting and resolving. Also, it was evaluated the TAG profile of Z. morio larvae due to their highest oil content. The results showed a high oleic acid (OA, 18:1n9) content, which displays modulatory effects in a wide range of physiological functions, having anti-inflammatory and anti-atherogenic properties. In conclusion, this study clearly shows that Z. morio and H. illucens larvae constitute an alternative source of OA- and ALA-rich oils, respectively, which can be devoted for food use, as well as for using in the food and pharmaceutical industries, with agronomic implications. Finally, although the profile of Z. morio was not improved with fruit feeding, this kind of feeding could be used due to its low environmental impact.

Keywords: fatty acids, fruit byproducts, Hermetia illucens, Zophoba morio, Tenebrio molitor, insect rearing

Procedia PDF Downloads 147

Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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Authors: Jana Abu Ahmada, Zaineb Mohamed, Ilyasse Aksikas

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The linear quadratic control system of hyperbolic first order partial differential equations (PDEs) are presented. The aim of this research is to control chemical reactions. This is achieved by converting the PDEs system to ordinary differential equations (ODEs) using the method of characteristics to reduce the system to control it by using the integral reinforcement learning. The designed controller is applied to a catalytic cracking reactor. Background—Transport-Reaction systems cover a large chemical and bio-chemical processes. They are best described by nonlinear PDEs derived from mass and energy balances. As a main application to be considered in this work is the catalytic cracking reactor. Indeed, the cracking reactor is widely used to convert high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils into more valuable gasoline, olefinic gases, and others. On the other hand, control of PDEs systems is an important and rich area of research. One of the main control techniques is feedback control. This type of control utilizes information coming from the system to correct its trajectories and drive it to a desired state. Moreover, feedback control rejects disturbances and reduces the variation effects on the plant parameters. Linear-quadratic control is a feedback control since the developed optimal input is expressed as feedback on the system state to exponentially stabilize and drive a linear plant to the steady-state while minimizing a cost criterion. The integral reinforcement learning policy iteration technique is a strong method that solves the linear quadratic regulator problem for continuous-time systems online in real time, using only partial information about the system dynamics (i.e. the drift dynamics A of the system need not be known), and without requiring measurements of the state derivative. This is, in effect, a direct (i.e. no system identification procedure is employed) adaptive control scheme for partially unknown linear systems that converges to the optimal control solution. Contribution—The goal of this research is to Develop a characteristics-based optimal controller for a class of hyperbolic PDEs and apply the developed controller to a catalytic cracking reactor model. In the first part, developing an algorithm to control a class of hyperbolic PDEs system will be investigated. The method of characteristics will be employed to convert the PDEs system into a system of ODEs. Then, the control problem will be solved along the characteristic curves. The reinforcement technique is implemented to find the state-feedback matrix. In the other half, applying the developed algorithm to the important application of a catalytic cracking reactor. The main objective is to use the inlet fraction of gas oil as a manipulated variable to drive the process state towards desired trajectories. The outcome of this challenging research would yield the potential to provide a significant technological innovation for the gas industries since the catalytic cracking reactor is one of the most important conversion processes in petroleum refineries.

Keywords: PDEs, reinforcement iteration, method of characteristics, riccati equation, cracking reactor

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Authors: Aurora Sheehy, Caitlin Prince

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Within current orthodox medical protocols, trauma and mental health issues are deemed to reside within the realm of cognitive or psychological therapists and are marginalised in these areas, in part due to limited drugs option available, mostly manipulating neurotransmitters or sedating patients to reduce symptoms. By contrast, this research presents examples from the clinical practice of how trauma can be assessed and treated physiologically. Adverse Childhood Experiences (ACEs) are a tally of different types of abuse and neglect. It has been used as a measurable and reliable predictor of the likelihood of the development of autoimmune disease. It is a direct way to demonstrate reliably the health impact of traumatic life experiences. A second assessment tool is Allostatic Load, which refers to the cumulative effects that chronic stress has on mental and physical health. It records the decline of an individual’s physiological capacity to cope with their experience. It uses a specific grouping of serum testing and physical measures. It includes an assessment of neuroendocrine, cardiovascular, immune and metabolic systems. Allostatic load demonstrates the health impact that trauma has throughout the body. It forms part of an initial intake assessment in clinical practice and could also be used in research to evaluate treatment. Examining medicinal plants for their physiological, neurological and somatic effects through the lens of Polyvagal theory offers new opportunities for trauma treatments. In situations where Polyvagal theory recommends activities and exercises to enable parasympathetic activation, many herbs that affect Effector Memory T (TEM) cells also enact these responses. Traditional or Indigenous European herbs show the potential to support the polyvagal tone, through multiple mechanisms. As the ventral vagal nerve reaches almost every major organ, plants that have actions on these tissues can be understood via their polyvagal actions, such as monoterpenes as agents to improve respiratory vagal tone, cyanogenic glycosides to reset polyvagal tone, volatile oils rich in phenyl methyl esters improve both sympathetic and parasympathetic tone, bitters activate gut function and can strongly promote parasympathetic regulation. Auricular Acupuncture uses a system of somatotopic mapping of the auricular surface overlaid with an image of an inverted foetus with each body organ and system featured. Given that the concha of the auricle is the only place on the body where the Vagus Nerve neurons reach the surface of the skin, several investigators have evaluated non-invasive, transcutaneous electrical nerve stimulation (TENS) at auricular points. Drawn from an interdisciplinary evidence base and developed through clinical practice, these assessment and treatment tools are examples of practitioners in the field innovating out of necessity for the best outcomes for patients. This paper draws on case studies to direct future research.

Keywords: polyvagal, auricular acupuncture, trauma, herbs

Procedia PDF Downloads 93

Authors: Mohamad Saab, Florent Real, Francois Virot, Laurent Cantrel, Valerie Vallet

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All spent nuclear fuel reprocessing plants use the PUREX process (Plutonium Uranium Refining by Extraction), which is a liquid-liquid extraction method. The organic extracting solvent is a mixture of tri-n-butyl phosphate (TBP) and hydrocarbon solvent such as hydrogenated tetra-propylene (TPH). By chemical complexation, uranium and plutonium (from spent fuel dissolved in nitric acid solution), are separated from fission products and minor actinides. During a normal extraction operation, uranium is extracted in the organic phase as the UO₂(NO₃)₂(TBP)₂ complex. The TBP solvent can form an explosive mixture called red oil when it comes in contact with nitric acid. The formation of this unstable organic phase originates from the reaction between TBP and its degradation products on the one hand, and nitric acid, its derivatives and heavy metal nitrate complexes on the other hand. The decomposition of the red oil can lead to violent explosive thermal runaway. These hazards are at the origin of several accidents such as the two in the United States in 1953 and 1975 (Savannah River) and, more recently, the one in Russia in 1993 (Tomsk). This raises the question of the exothermicity of reactions that involve TBP and all other degradation products, and calls for a better knowledge of the underlying chemical phenomena. A simulation tool (Alambic) is currently being developed at IRSN that integrates thermal and kinetic functions related to the deterioration of uranyl nitrates in organic and aqueous phases, but not of the n-butyl phosphate. To include them in the modeling scheme, there is an urgent need to obtain the thermodynamic and kinetic functions governing the deterioration processes in liquid phase. However, little is known about the thermodynamic properties, like standard enthalpies of formation, of the n-butyl phosphate molecules and of the UO₂(NO₃)₂(TBP)₂ UO₂(NO₃)₂(HDBP)(TBP) and UO₂(NO₃)₂(HDBP)₂ complexes. In this work, we propose to estimate the thermodynamic properties with Quantum Methods (QM). Thus, in the first part of our project, we focused on the mono, di, and tri-butyl complexes. Quantum chemical calculations have been performed to study several reactions leading to the formation of mono-(H₂MBP), di-(HDBP), and TBP in gas and liquid phases. In the gas phase, the optimal structures of all species were optimized using the B3LYP density functional. Triple-ζ def2-TZVP basis sets were used for all atoms. All geometries were optimized in the gas-phase, and the corresponding harmonic frequencies were used without scaling to compute the vibrational partition functions at 298.15 K and 0.1 Mpa. Accurate single point energies were calculated using the efficient localized LCCSD(T) method to the complete basis set limit. Whenever species in the liquid phase are considered, solvent effects are included with the COSMO-RS continuum model. The standard enthalpies of formation of TBP, HDBP, and H2MBP are finally predicted with an uncertainty of about 15 kJ mol⁻¹. In the second part of this project, we have investigated the fundamental properties of three organic species that mostly contribute to the thermal runaway: UO₂(NO₃)₂(TBP)₂, UO₂(NO₃)₂(HDBP)(TBP), and UO₂(NO₃)₂(HDBP)₂ using the same quantum chemical methods that were used for TBP and its derivatives in both the gas and the liquid phase. We will discuss the structures and thermodynamic properties of all these species.

Keywords: PUREX process, red oils, quantum chemical methods, hydrolysis

Procedia PDF Downloads 189