Search results for: CO₂ adsorption
60 An Overview of PFAS Treatment Technologies with an In-Depth Analysis of Two Case Studies
Authors: Arul Ayyaswami, Vidhya Ramalingam
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Per- and polyfluoroalkyl substances (PFAS) have emerged as a significant environmental concern due to their ubiquity and persistence in the environment. Their chemical characteristics and adverse effects on human health demands more effective and sustainable solutions in remediation of the PFAS. The work presented here encompasses an overview of treatment technologies with two case studies that utilize effective approaches in addressing PFAS contaminated media. Currently the options for treatment of PFAS compounds include Activated carbon adsorption, Ion Exchange, Membrane Filtration, Advanced oxidation processes, Electrochemical treatment, and Precipitation and Coagulation. In the first case study, a pilot study application of colloidal activated carbon (CAC) was completed to address PFAS from aqueous film-forming foam (AFFF) used to extinguish a large fire. The pilot study was used to demonstrate the effectiveness of a CAC in situ permeable reactive barrier (PRB) in effectively stopping the migration of PFOS and PFOA, moving from the source area at high concentrations. Before the CAC PRB installation, an injection test using - fluorescein dye was conducted to determine the primary fracture-induced groundwater flow pathways. A straddle packer injection delivery system was used to isolate discrete intervals and gain resolution over the 70 feet saturated zone targeted for treatment. Flow rates were adjusted, and aquifer responses were recorded for each interval. The results from the injection test were used to design the pilot test injection plan using CAC PRB. Following the CAC PRB application, the combined initial concentration 91,400 ng/L of PFOS and PFOA were reduced to approximately 70 ng/L (99.9% reduction), after only one month following the injection event. The results demonstrate the remedy's effectiveness to quickly and safely contain high concentrations of PFAS in fractured bedrock, reducing the risk to downgradient receptors. The second study involves developing a reductive defluorination treatment process using UV and electron acceptor. This experiment indicates a significant potential in treatment of PFAS contaminated waste media such as landfill leachates. The technology also shows a promising way of tacking these contaminants without the need for secondary waste disposal or any additional pre-treatments.Keywords: per- and polyfluoroalkyl substances (PFAS), colloidal activated carbon (CAC), destructive PFAS treatment technology, aqueous film-forming foam (AFFF)
Procedia PDF Downloads 5459 Vapour Liquid Equilibrium Measurement of CO₂ Absorption in Aqueous 2-Aminoethylpiperazine (AEP)
Authors: Anirban Dey, Sukanta Kumar Dash, Bishnupada Mandal
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Carbondioxide (CO2) is a major greenhouse gas responsible for global warming and fossil fuel power plants are the main emitting sources. Therefore the capture of CO2 is essential to maintain the emission levels according to the standards. Carbon capture and storage (CCS) is considered as an important option for stabilization of atmospheric greenhouse gases and minimizing global warming effects. There are three approaches towards CCS: Pre combustion capture where carbon is removed from the fuel prior to combustion, Oxy-fuel combustion, where coal is combusted with oxygen instead of air and Post combustion capture where the fossil fuel is combusted to produce energy and CO2 is removed from the flue gases left after the combustion process. Post combustion technology offers some advantage as existing combustion technologies can still be used without adopting major changes on them. A number of separation processes could be utilized part of post –combustion capture technology. These include (a) Physical absorption (b) Chemical absorption (c) Membrane separation (d) Adsorption. Chemical absorption is one of the most extensively used technologies for large scale CO2 capture systems. The industrially important solvents used are primary amines like Monoethanolamine (MEA) and Diglycolamine (DGA), secondary amines like diethanolamine (DEA) and Diisopropanolamine (DIPA) and tertiary amines like methyldiethanolamine (MDEA) and Triethanolamine (TEA). Primary and secondary amines react fast and directly with CO2 to form stable carbamates while Tertiary amines do not react directly with CO2 as in aqueous solution they catalyzes the hydrolysis of CO2 to form a bicarbonate ion and a protonated amine. Concentrated Piperazine (PZ) has been proposed as a better solvent as well as activator for CO2 capture from flue gas with a 10 % energy benefit compared to conventional amines such as MEA. However, the application of concentrated PZ is limited due to its low solubility in water at low temperature and lean CO2 loading. So following the performance of PZ its derivative 2-Aminoethyl piperazine (AEP) which is a cyclic amine can be explored as an activator towards the absorption of CO2. Vapour liquid equilibrium (VLE) in CO2 capture systems is an important factor for the design of separation equipment and gas treating processes. For proper thermodynamic modeling accurate equilibrium data for the solvent system over a wide range of temperatures, pressure and composition is essential. The present work focuses on the determination of VLE data for (AEP + H2O) system at 40 °C for various composition range.Keywords: absorption, aminoethyl piperazine, carbondioxide, vapour liquid equilibrium
Procedia PDF Downloads 26158 Lithium and Sodium Ion Capacitors with High Energy and Power Densities based on Carbons from Recycled Olive Pits
Authors: Jon Ajuria, Edurne Redondo, Roman Mysyk, Eider Goikolea
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Hybrid capacitor configurations are now of increasing interest to overcome the current energy limitations of supercapacitors entirely based on non-Faradaic charge storage. Among them, Li-ion capacitors including a negative battery-type lithium intercalation electrode and a positive capacitor-type electrode have achieved tremendous progress and have gone up to commercialization. Inexpensive electrode materials from renewable sources have recently received increased attention since cost is a persistently major criterion to make supercapacitors a more viable energy solution, with electrode materials being a major contributor to supercapacitor cost. Additionally, Na-ion battery chemistries are currently under development as less expensive and accessible alternative to Li-ion based battery electrodes. In this work, we are presenting both lithium and sodium ion capacitor (LIC & NIC) entirely based on electrodes prepared from carbon materials derived from recycled olive pits. Yearly, around 1 million ton of olive pit waste is generated worldwide, of which a third originates in the Spanish olive oil industry. On the one hand, olive pits were pyrolized at different temperatures to obtain a low specific surface area semigraphitic hard carbon to be used as the Li/Na ion intercalation (battery-type) negative electrode. The best hard carbon delivers a total capacity of 270mAh/g vs Na/Na+ in 1M NaPF6 and 350mAh/g vs Li/Li+ in 1M LiPF6. On the other hand, the same hard carbon is chemically activated with KOH to obtain high specific surface area -about 2000 m2g-1- activated carbon that is further used as the ion-adsorption (capacitor-type) positive electrode. In a voltage window of 1.5-4.2V, activated carbon delivers a specific capacity of 80 mAh/g vs. Na/Na+ and 95 mAh/g vs. Li/Li+ at 0.1A /g. Both electrodes were assembled in the same hybrid cell to build a LIC/NIC. For comparison purposes, a symmetric EDLC supercapacitor cell using the same activated carbon in 1.5M Et4NBF4 electrolyte was also built. Both LIC & NIC demonstrates considerable improvements in the energy density over its EDLC counterpart, delivering a maximum energy density of 110Wh/Kg at a power density of 30W/kg AM and a maximum power density of 6200W/Kg at an energy density of 27 Wh/Kg in the case of NIC and a maximum energy density of 110Wh/Kg at a power density of 30W/kg and a maximum power density of 18000W/Kg at an energy density of 22 Wh/Kg in the case of LIC. In conclusion, our work demonstrates that the same biomass waste can be adapted to offer a hybrid capacitor/battery storage device overcoming the limited energy density of corresponding double layer capacitors.Keywords: hybrid supercapacitor, Na-Ion capacitor, supercapacitor, Li-Ion capacitor, EDLC
Procedia PDF Downloads 19557 Influence of Confinement on Phase Behavior in Unconventional Gas Condensate Reservoirs
Authors: Szymon Kuczynski
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Poland is characterized by the presence of numerous sedimentary basins and hydrocarbon provinces. Since 2006 exploration for hydrocarbons in Poland become gradually more focus on new unconventional targets, particularly on the shale gas potential of the Upper Ordovician and Lower Silurian in the Baltic-Podlasie-Lublin Basin. The first forecast prepared by US Energy Information Administration in 2011 indicated to 5.3 Tcm of natural gas. In 2012, Polish Geological Institute presented its own forecast which estimated maximum reserves on 1.92 Tcm. The difference in the estimates was caused by problems with calculations of the initial amount of adsorbed, as well as free, gas trapped in shale rocks (GIIP - Gas Initially in Place). This value is dependent from sorption capacity, gas saturation and mutual interactions between gas, water, and rock. Determination of the reservoir type in the initial exploration phase brings essential knowledge, which has an impact on decisions related to the production. The study of porosity impact for phase envelope shift eliminates errors and improves production profitability. Confinement phenomenon affects flow characteristics, fluid properties, and phase equilibrium. The thermodynamic behavior of confined fluids in porous media is subject to the basic considerations for industrial applications such as hydrocarbons production. In particular the knowledge of the phase equilibrium and the critical properties of the contained fluid is essential for the design and optimization of such process. In pores with a small diameter (nanopores), the effect of the wall interaction with the fluid particles becomes significant and occurs in shale formations. Nano pore size is similar to the fluid particles’ diameter and the area of particles which flow without interaction with pore wall is almost equal to the area where this phenomenon occurs. The molecular simulation studies have shown an effect of confinement to the pseudo critical properties. Therefore, the critical parameters pressure and temperature and the flow characteristics of hydrocarbons in terms of nano-scale are under the strong influence of fluid particles with the pore wall. It can be concluded that the impact of a single pore size is crucial when it comes to the nanoscale because there is possible the above-described effect. Nano- porosity makes it difficult to predict the flow of reservoir fluid. Research are conducted to explain the mechanisms of fluid flow in the nanopores and gas extraction from porous media by desorption.Keywords: adsorption, capillary condensation, phase envelope, nanopores, unconventional natural gas
Procedia PDF Downloads 33056 Biosorption of Nickel by Penicillium simplicissimum SAU203 Isolated from Indian Metalliferous Mining Overburden
Authors: Suchhanda Ghosh, A. K. Paul
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Nickel, an industrially important metal is not mined in India, due to the lack of its primary mining resources. But, the chromite deposits occurring in the Sukinda and Baula-Nuasahi region of Odhisa, India, is reported to contain around 0.99% of nickel entrapped in the goethite matrix of the lateritic iron rich ore. Weathering of the dumped chromite mining overburden often leads to the contamination of the ground as well as the surface water with toxic nickel. Microbes inherent to this metal contaminated environment are reported to be capable of removal as well as detoxification of various metals including nickel. Nickel resistant fungal isolates obtained in pure form from the metal rich overburden were evaluated for their potential to biosorb nickel by using their dried biomass. Penicillium simplicissimum SAU203 was the best nickel biosorbant among the 20 fungi tested and was capable to sorbing 16.85 mg Ni/g biomass from a solution containing 50 mg/l of Ni. The identity of the isolate was confirmed using 18S rRNA gene analysis. The sorption capacity of the isolate was further standardized following Langmuir and Freundlich adsorption isotherm models and the results reflected energy efficient sorption. Fourier-transform infrared spectroscopy studies of the nickel loaded and control biomass in a comparative basis revealed the involvement of hydroxyl, amine and carboxylic groups in Ni binding. The sorption process was also optimized for several standard parameters like initial metal ion concentration, initial sorbet concentration, incubation temperature and pH, presence of additional cations and pre-treatment of the biomass by different chemicals. Optimisation leads to significant improvements in the process of nickel biosorption on to the fungal biomass. P. simplicissimum SAU203 could sorb 54.73 mg Ni/g biomass with an initial Ni concentration of 200 mg/l in solution and 21.8 mg Ni/g biomass with an initial biomass concentration of 1g/l solution. Optimum temperature and pH for biosorption was recorded to be 30°C and pH 6.5 respectively. Presence of Zn and Fe ions improved the sorption of Ni(II), whereas, cobalt had a negative impact. Pre-treatment of biomass with various chemical and physical agents has affected the proficiency of Ni sorption by P. simplicissimum SAU203 biomass, autoclaving as well as treatment of biomass with 0.5 M sulfuric acid and acetic acid reduced the sorption as compared to the untreated biomass, whereas, NaOH and Na₂CO₃ and Twin 80 (0.5 M) treated biomass resulted in augmented metal sorption. Hence, on the basis of the present study, it can be concluded that P. simplicissimum SAU203 has the potential for the removal as well as detoxification of nickel from contaminated environments in general and particularly from the chromite mining areas of Odhisa, India.Keywords: nickel, fungal biosorption, Penicillium simplicissimum SAU203, Indian chromite mines, mining overburden
Procedia PDF Downloads 18555 Electrochemical Corrosion and Mechanical Properties of Structural Materials for Oil and Gas Applications in Simulated Deep-Sea Well Environments
Authors: Turin Datta, Kisor K. Sahu
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Structural materials used in today’s oil and gas exploration and drilling of both onshore and offshore oil and gas wells must possess superior tensile properties, excellent resistance to corrosive degradation that includes general, localized (pitting and crevice) and environment assisted cracking such as stress corrosion cracking and hydrogen embrittlement. The High Pressure and High Temperature (HPHT) wells are typically operated at temperature and pressure that can exceed 300-3500F and 10,000psi (69MPa) respectively which necessitates the use of exotic materials in these exotic sources of natural resources. This research investigation is focussed on the evaluation of tensile properties and corrosion behavior of AISI 4140 High-Strength Low Alloy Steel (HSLA) possessing tempered martensitic microstructure and Duplex 2205 Stainless Steel (DSS) having austenitic and ferritic phase. The selection of this two alloys are primarily based on economic considerations as 4140 HSLA is cheaper when compared to DSS 2205. Due to the harsh aggressive chemical species encountered in deep oil and gas wells like chloride ions (Cl-), carbon dioxide (CO2), hydrogen sulphide (H2S) along with other mineral organic acids, DSS 2205, having a dual-phase microstructure can mitigate the degradation resulting from the presence of both chloride ions (Cl-) and hydrogen simultaneously. Tensile properties evaluation indicates a ductile failure of DSS 2205 whereas 4140 HSLA exhibit quasi-cleavage fracture due to the phenomenon of ‘tempered martensitic embrittlement’. From the potentiodynamic polarization testing, it is observed that DSS 2205 has higher corrosion resistance than 4140 HSLA; the former exhibits passivity signifying resistance to localized corrosion while the latter exhibits active dissolution in all the environmental parameters space that was tested. From the Scanning Electron Microscopy (SEM) evaluation, it is understood that stable pits appear in DSS 2205 only when the temperature exceeds the critical pitting temperature (CPT). SEM observation of the corroded 4140 HSLA specimen tested in aqueous 3.5 wt.% NaCl solution reveals intergranular cracking which appears due to the adsorption and diffusion of hydrogen during polarization, thus, causing hydrogen-induced cracking/hydrogen embrittlement. General corrosion testing of DSS 2205 in acidic brine (pH~3.0) solution at ambient temperature using coupons indicate no weight loss even after three months whereas the corrosion rate of AISI 4140 HSLA is significantly higher after one month of testing.Keywords: DSS 2205, polarization, pitting, SEM
Procedia PDF Downloads 26254 Studies of Heavy Metal Ions Removal Efficiency in the Presence of Anionic Surfactant Using Ion Exchangers
Authors: Anna Wolowicz, Katarzyna Staszak, Zbigniew Hubicki
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Nowadays heavy metal ions as well as surfactants are widely used throughout the world due to their useful properties. The consequence of such widespread use is their significant production. On the other hand, the increasing demand for surfactants and heavy metal ions results in production of large amounts of wastewaters which are discharged to the environment from mining, metal plating, pharmaceutical, cosmetic, fertilizer, paper, pesticide and electronic industries, pigments producing, petroleum refining and from autocatalyst, fibers, food, polymer industries etc. Heavy metal ions are non-biodegradable in the environment, cable of accumulation in living organisms and organs, toxic and carcinogenic. On the other hand, not only heavy metal ions but also surfactants affect the purity of water and soils. Some of surfactants are also toxic, harmful and dangerous because they are able to penetrate into surface waters causing foaming, blocked diffusion of oxygen from the atmosphere and act as emulsifiers of hydrophobic substances and increase solubility of many the dangerous pollutants. Among surfactants the anionic ones dominate and their share in the global production of surfactants is around 50 ÷ 60%. Due to the negative impact of heavy metals and surfactants on aquatic ecosystems and living organisms, removal and monitoring of their concentration in the environment is extremely important. Surfactants and heavy metal ions removal can be achieved by different biological and physicochemical methods. The adsorption as well as the ion-exchange methods play here a significant role. The aim of this study was heavy metal ions removal from aqueous solutions using different types of ion exchangers in the presence of anionic surfactants. Preliminary studies of copper(II), nickel(II), zinc(II) and cobalt(II) removal from acidic solutions using ion exchangers (Lewatit MonoPlus TP 220, Lewatit MonoPlus SR 7, Purolite A 400 TL, Purolite A 830, Purolite S 984, Dowex PSR 2, Dowex PSR3, Lewatit AF-5) allowed to select the most effective ones for the above mentioned sorbates and then to checking their removal efficiency in the presence of anionic surfactants. As it was found out Lewatit MonoPlus TP 220 of the chelating type, show the highest sorption capacities for copper(II) ions in comparison with the other ion exchangers under discussion, e.g. 9.98 mg/g (0.1 M HCl); 9.12 mg/g (6 M HCl). Moreover, cobalt(II) removal efficiency was the highest in 0.1 M HCl using also Lewatit MonoPlus TP 220 (6.9 mg/g) similar to zinc(II) (9.1 mg/g) and nickiel(II) (6.2 mg/g). As the anionic surfactant sodium dodecyl sulphate (SDS) was used and surfactant parameters such as viscosity (η), density (ρ) and critical micelle concentration (CMC) were obtained: η = 1.13 ± 0,01 mPa·s; ρ = 999.76 mg/cm3; CMC = 2.26 g/cm3. The studies of copper(II) removal from acidic solutions in the presence of SDS of different concentration show negligible effects on copper(II) removal efficiency. The sorption capacity of Cu(II) from 0.1 M acidic solution of 500 mg/L initial concentration was equal to 46.8 mg/g whereas in the presence of SDS 45.3 mg/g (0.1 mg SDS/L), 47.1 mg/g (0.5 mg SDS/L), 46.6 mg/g (1 mg SDS/L).Keywords: anionic surfactant, heavy metal ions, ion exchanger, removal
Procedia PDF Downloads 13653 Degradation Kinetics of Cardiovascular Implants Employing Full Blood and Extra-Corporeal Circulation Principles: Mimicking the Human Circulation In vitro
Authors: Sara R. Knigge, Sugat R. Tuladhar, Hans-Klaus HöFfler, Tobias Schilling, Tim Kaufeld, Axel Haverich
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Tissue engineered (TE) heart valves based on degradable electrospun fiber scaffold represent a promising approach to overcome the known limitations of mechanical or biological prostheses. But the mechanical stress in the high-pressure system of the human circulation is a severe challenge for the delicate materials. Hence, the prediction of the scaffolds` in vivo degradation kinetics must be as accurate as possible to prevent fatal events in future animal or even clinical trials. Therefore, this study investigates whether long-term testing in full blood provides more meaningful results regarding the degradation behavior than conventional tests in simulated body fluids (SBF) or Phosphate Buffered Saline (PBS). Fiber mats were produced from a polycaprolactone (PCL)/tetrafluoroethylene solution by electrospinning. The morphology of the fiber mats was characterized via scanning electron microscopy (SEM). A maximum physiological degradation environment utilizing a test set-up with porcine full blood was established. The set-up consists of a reaction vessel, an oxygenator unit, and a roller pump. The blood parameters (pO2, pCO2, temperature, and pH) were monitored with an online test system. All tests were also carried out in the test circuit with SBF and PBS to compare conventional degradation media with the novel full blood setting. The polymer's degradation is quantified by SEM picture analysis, differential scanning calorimetry (DSC), and Raman spectroscopy. Tensile and cyclic loading tests were performed to evaluate the mechanical integrity of the scaffold. Preliminary results indicate that PCL degraded slower in full blood than in SBF and PBS. The uptake of water is more pronounced in the full blood group. Also, PCL preserved its mechanical integrity longer when degraded in full blood. Protein absorption increased during the degradation process. Red blood cells, platelets, and their aggregates adhered on the PCL. Presumably, the degradation led to a more hydrophilic polymeric surface which promoted the protein adsorption and the blood cell adhesion. Testing degradable implants in full blood allows for developing more reliable scaffold materials in the future. Material tests in small and large animal trials thereby can be focused on testing candidates that have proven to function well in an in-vivo-like setting.Keywords: Electrospun scaffold, full blood degradation test, long-term polymer degradation, tissue engineered aortic heart valve
Procedia PDF Downloads 14152 Carbon Capture and Storage Using Porous-Based Aerogel Materials
Authors: Rima Alfaraj, Abeer Alarawi, Murtadha AlTammar
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The global energy landscape heavily relies on the oil and gas industry, which faces the critical challenge of reducing its carbon footprint. To address this issue, the integration of advanced materials like aerogels has emerged as a promising solution to enhance sustainability and environmental performance within the industry. This study thoroughly examines the application of aerogel-based technologies in the oil and gas sector, focusing particularly on their role in carbon capture and storage (CCS) initiatives. Aerogels, known for their exceptional properties, such as high surface area, low density, and customizable pore structure, have garnered attention for their potential in various CCS strategies. The review delves into various fabrication techniques utilized in producing aerogel materials, including sol-gel, supercritical drying, and freeze-drying methods, to assess their suitability for specific industry applications. Beyond fabrication, the practicality of aerogel materials in critical areas such as flow assurance, enhanced oil recovery, and thermal insulation is explored. The analysis spans a wide range of applications, from potential use in pipelines and equipment to subsea installations, offering valuable insights into the real-world implementation of aerogels in the oil and gas sector. The paper also investigates the adsorption and storage capabilities of aerogel-based sorbents, showcasing their effectiveness in capturing and storing carbon dioxide (CO₂) molecules. Optimization of pore size distribution and surface chemistry is examined to enhance the affinity and selectivity of aerogels towards CO₂, thereby improving the efficiency and capacity of CCS systems. Additionally, the study explores the potential of aerogel-based membranes for separating and purifying CO₂ from oil and gas streams, emphasizing their role in the carbon capture and utilization (CCU) value chain in the industry. Emerging trends and future perspectives in integrating aerogel-based technologies within the oil and gas sector are also discussed, including the development of hybrid aerogel composites and advanced functional components to further enhance material performance and versatility. By synthesizing the latest advancements and future directions in aerogel used for CCS applications in the oil and gas industry, this review offers a comprehensive understanding of how these innovative materials can aid in transitioning towards a more sustainable and environmentally conscious energy landscape. The insights provided can assist in strategic decision-making, drive technology development, and foster collaborations among academia, industry, and policymakers to promote the widespread adoption of aerogel-based solutions in the oil and gas sector.Keywords: CCS, porous, carbon capture, oil and gas, sustainability
Procedia PDF Downloads 2651 Enhancing Air Quality: Investigating Filter Lifespan and Byproducts in Air Purification Solutions
Authors: Freja Rydahl Rasmussen, Naja Villadsen, Stig Koust
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Air purifiers have become widely implemented in a wide range of settings, including households, schools, institutions, and hospitals, as they tackle the pressing issue of indoor air pollution. With their ability to enhance indoor air quality and create healthier environments, air purifiers are particularly vital when ventilation options are limited. These devices incorporate a diverse array of technologies, including HEPA filters, active carbon filters, UV-C light, photocatalytic oxidation, and ionizers, each designed to combat specific pollutants and improve air quality within enclosed spaces. However, the safety of air purifiers has not been investigated thoroughly, and many questions still arise when applying them. Certain air purification technologies, such as UV-C light or ionization, can unintentionally generate undesirable byproducts that can negatively affect indoor air quality and health. It is well-established that these technologies can inadvertently generate nanoparticles or convert common gaseous compounds into harmful ones, thus exacerbating air pollution. However, the formation of byproducts can vary across products, necessitating further investigation. There is a particular concern about the formation of the carcinogenic substance formaldehyde from common gases like acetone. Many air purifiers use mechanical filtration to remove particles, dust, and pollen from the air. Filters need to be replaced periodically for optimal efficiency, resulting in an additional cost for end-users. Currently, there are no guidelines for filter lifespan, and replacement recommendations solely rely on manufacturers. A market screening revealed that manufacturers' recommended lifespans vary greatly (from 1 month to 10 years), and there is a need for general recommendations to guide consumers. Activated carbon filters are used to adsorb various types of chemicals that can pose health risks or cause unwanted odors. These filters have a certain capacity before becoming saturated. If not replaced in a timely manner, the adsorbed substances are likely to be released from the filter through off-gassing or losing adsorption efficiency. The goal of this study is to investigate the lifespan of filters as well as investigate the potentially harmful effects of air purifiers. Understanding the lifespan of filters used in air purifiers and the potential formation of harmful byproducts is essential for ensuring their optimal performance, guiding consumers in their purchasing decisions, and establishing industry standards for safer and more effective air purification solutions. At this time, a selection of air purifiers has been chosen, and test methods have been established. In the following 3 months, the tests will be conducted, and the results will be ready for presentation later.Keywords: air purifiers, activated carbon filters, byproducts, clean air, indoor air quality
Procedia PDF Downloads 6450 Co-pyrolysis of Sludge and Kaolin/Zeolite to Stabilize Heavy Metals
Authors: Qian Li, Zhaoping Zhong
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Sewage sludge, a typical solid waste, has inevitably been produced in enormous quantities in China. Still worse, the amount of sewage sludge produced has been increasing due to rapid economic development and urbanization. Compared to the conventional method to treat sewage sludge, pyrolysis has been considered an economic and ecological technology because it can significantly reduce the sludge volume, completely kill pathogens, and produce valuable solid, gas, and liquid products. However, the large-scale utilization of sludge biochar has been limited due to the considerable risk posed by heavy metals in the sludge. Heavy metals enriched in pyrolytic biochar could be divided into exchangeable, reducible, oxidizable, and residual forms. The residual form of heavy metals is the most stable and cannot be used by organisms. Kaolin and zeolite are environmentally friendly inorganic minerals with a high surface area and heat resistance characteristics. So, they exhibit the enormous potential to immobilize heavy metals. In order to reduce the risk of leaching heavy metals in the pyrolysis biochar, this study pyrolyzed sewage sludge mixed with kaolin/zeolite in a small rotary kiln. The influences of additives and pyrolysis temperature on the leaching concentration and morphological transformation of heavy metals in pyrolysis biochar were investigated. The potential mechanism of stabilizing heavy metals in the co-pyrolysis of sludge blended with kaolin/zeolite was explained by scanning electron microscopy, X-ray diffraction, and specific surface area and porosity analysis. The European Community Bureau of Reference sequential extraction procedure has been applied to analyze the forms of heavy metals in sludge and pyrolysis biochar. All the concentrations of heavy metals were examined by flame atomic absorption spectrophotometry. Compared with the proportions of heavy metals associated with the F4 fraction in pyrolytic carbon prepared without additional agents, those in carbon obtained by co-pyrolysis of sludge and kaolin/zeolite increased. Increasing the additive dosage could improve the proportions of the stable fraction of various heavy metals in biochar. Kaolin exhibited a better effect on stabilizing heavy metals than zeolite. Aluminosilicate additives with excellent adsorption performance could capture more released heavy metals during sludge pyrolysis. Then heavy metal ions would react with the oxygen ions of additives to form silicate and aluminate, causing the conversion of heavy metals from unstable fractions (sulfate, chloride, etc.) to stable fractions (silicate, aluminate, etc.). This study reveals that the efficiency of stabilizing heavy metals depends on the formation of stable mineral compounds containing heavy metals in pyrolysis biochar.Keywords: co-pyrolysis, heavy metals, immobilization mechanism, sewage sludge
Procedia PDF Downloads 6249 Amorphous Aluminophosphates: An Insight to the Changes in Structural Properties and Catalytic Activity by the Incorporation of Transition Metals
Authors: A. Hamza, H. Kathyayini, N. Nagaraju
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Aluminophosphates, both amorphous and crystalline materials find applications as adsorbents, ceramics, and pigments and as catalysts/catalyst supports in organic fine chemical synthesis. Most of the applications are varied depending on the type of metal incorporated, particle size, surface area, porosity and morphology of aluminophosphate. The porous and surface properties of these materials are normally fine-tuned by adopting various preparation methodologies. Numerous crystalline microporous and mesoporous aluminophosphates and metal-aluminophosphates have been reported in literature, in which the synthesis has been carried out by using structure directing organic molecules/surfactants. In present work, amorphous aluminophosphate (AlP) and metal-aluminophosphates MAlP (M = Cu, Zn, Cr, Fe, Ce and Zr) and their mixed forms M-1M2AlP are prepared under a typical precipitation condition, i.e. at low temperature in order to keep the Von-Weirmann relative super saturation of the precipitating medium and obtain small size precipitate particles. These materials are prepared without using any surfactants. All materials are thoroughly characterised for surface and bulk properties by N2 adsorption-desorption technique, XRD, FT-IR, TG and SEM. The materials are also analysed for the amount and the strength of their surface acid sites, by NH3-TPD and CO2-TPD techniques respectively. All the materials prepared in the work are investigated for their catalytic activity in following applications in the synthesis of industrially important Jasminaldehyde via, aldol condensation of n-heptanal and benzaldehyde, in the synthesis of biologically important chalcones by Claisen-shmidth condensation of benzaldehyde and substituted chalcones. The effect of the amount of the catalysts, duration of the reaction, temperature of the reaction, molar ratio of the reactants has been studied. The porosity of pure aluminophosphate is found to be changed significantly by the incorporation of transition metals during preparation of aluminophosphate. The pore size increased from microporous to mesoporous and finally to macroporous by following order of metals Cu = Zn < Cr < Ce < Fe = Zr. The change in surface area and porosity of double metal-aluminophosphates depended on the concentration of both the metals. The acidity of aluminophosphate is either increased or decreased which depended on the type and valence of metals loaded. A good number of basic sites are created in metal-aluminophosphates irrespective of the metals used. A maximum catalytic activity for synthesis of both jasminaldehyde and chalcone is obtained by FeAlP as catalysts; these materials are characterized by decreased strength and concentration of acidic sites with optimum level basic sites.Keywords: amorphous metal-aluminophosphates, surface properties, acidic-basic properties, Aldol, Claisen-Shmidth condensation, jasminaldehyde, chalcone
Procedia PDF Downloads 29848 Corrosion Protection and Failure Mechanism of ZrO₂ Coating on Zirconium Alloy Zry-4 under Varied LiOH Concentrations in Lithiated Water at 360°C and 18.5 MPa
Authors: Guanyu Jiang, Donghai Xu, Huanteng Liu
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After the Fukushima-Daiichi accident, the development of accident tolerant fuel cladding materials to improve reactor safety has become a hot topic in the field of nuclear industry. ZrO₂ has a satisfactory neutron economy and can guarantee the fission chain reaction process, which enables it to be a promising coating for zirconium alloy cladding. Maintaining a good corrosion resistance in primary coolant loop during normal operations of Pressurized Water Reactors is a prerequisite for ZrO₂ as a protective coating on zirconium alloy cladding. Research on the corrosion performance of ZrO₂ coating in nuclear water chemistry is relatively scarce, and existing reports failed to provide an in-depth explanation for the failure causes of ZrO₂ coating. Herein, a detailed corrosion process of ZrO₂ coating in lithiated water at 360 °C and 18.5 MPa was proposed based on experimental research and molecular dynamics simulation. Lithiated water with different LiOH solutions in the present work was deaerated and had a dissolved oxygen concentration of < 10 ppb. The concentration of Li (as LiOH) was determined to be 2.3 ppm, 70 ppm, and 500 ppm, respectively. Corrosion tests were conducted in a static autoclave. Modeling and corresponding calculations were operated on Materials Studio software. The calculation of adsorption energy and dynamics parameters were undertaken by the Energy task and Dynamics task of the Forcite module, respectively. The protective effect and failure mechanism of ZrO₂ coating on Zry-4 under varied LiOH concentrations was further revealed by comparison with the coating corrosion performance in pure water (namely 0 ppm Li). ZrO₂ coating provided a favorable corrosion protection with the occurrence of localized corrosion at low LiOH concentrations. Factors influencing corrosion resistance mainly include pitting corrosion extension, enhanced Li+ permeation, short-circuit diffusion of O²⁻ and ZrO₂ phase transformation. In highly-concentrated LiOH solutions, intergranular corrosion, internal oxidation, and perforation resulted in coating failure. Zr ions were released to coating surface to form flocculent ZrO₂ and ZrO₂ clusters due to the strong diffusion and dissolution tendency of α-Zr in the Zry-4 substrate. Considering that primary water of Pressurized Water Reactors usually includes 2.3 ppm Li, the stability of ZrO₂ make itself a candidate fuel cladding coating material. Under unfavorable conditions with high Li concentrations, more boric acid should be added to alleviate caustic corrosion of ZrO₂ coating once it is used. This work can provide some references to understand the service behavior of nuclear coatings under variable water chemistry conditions and promote the in-pile application of ZrO₂ coating.Keywords: ZrO₂ coating, Zry-4, corrosion behavior, failure mechanism, LiOH concentration
Procedia PDF Downloads 7547 Effects of Drying and Extraction Techniques on the Profile of Volatile Compounds in Banana Pseudostem
Authors: Pantea Salehizadeh, Martin P. Bucknall, Robert Driscoll, Jayashree Arcot, George Srzednicki
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Banana is one of the most important crops produced in large quantities in tropical and sub-tropical countries. Of the total plant material grown, approximately 40% is considered waste and left in the field to decay. This practice allows fungal diseases such as Sigatoka Leaf Spot to develop, limiting plant growth and spreading spores in the air that can cause respiratory problems in the surrounding population. The pseudostem is considered a waste residue of production (60 to 80 tonnes/ha/year), although it is a good source of dietary fiber and volatile organic compounds (VOC’s). Strategies to process banana pseudostem into palatable, nutritious and marketable food materials could provide significant social and economic benefits. Extraction of VOC’s with desirable odor from dried and fresh pseudostem could improve the smell of products from the confectionary and bakery industries. Incorporation of banana pseudostem flour into bakery products could provide cost savings and improve nutritional value. The aim of this study was to determine the effects of drying methods and different banana species on the profile of volatile aroma compounds in dried banana pseudostem. The banana species analyzed were Musa acuminata and Musa balbisiana. Fresh banana pseudostem samples were processed by either freeze-drying (FD) or heat pump drying (HPD). The extraction of VOC’s was performed at ambient temperature using vacuum distillation and the resulting, mostly aqueous, distillates were analyzed using headspace solid phase microextraction (SPME) gas chromatography – mass spectrometry (GC-MS). Optimal SPME adsorption conditions were 50 °C for 60 min using a Supelco 65 μm PDMS/DVB Stableflex fiber1. Compounds were identified by comparison of their electron impact mass spectra with those from the Wiley 9 / NIST 2011 combined mass spectral library. The results showed that the two species have notably different VOC profiles. Both species contained VOC’s that have been established in literature to have pleasant appetizing aromas. These included l-Menthone, D-Limonene, trans-linlool oxide, 1-Nonanol, CIS 6 Nonen-1ol, 2,6 Nonadien-1-ol, Benzenemethanol, 4-methyl, 1-Butanol, 3-methyl, hexanal, 1-Propanol, 2-methyl- acid، 2-Methyl-2-butanol. Results show banana pseudostem VOC’s are better preserved by FD than by HPD. This study is still in progress and should lead to the optimization of processing techniques that would promote the utilization of banana pseudostem in the food industry.Keywords: heat pump drying, freeze drying, SPME, vacuum distillation, VOC analysis
Procedia PDF Downloads 32246 Polypyrrole as Bifunctional Materials for Advanced Li-S Batteries
Authors: Fang Li, Jiazhao Wang, Jianmin Ma
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The practical application of Li-S batteries is hampered due to poor cycling stability caused by electrolyte-dissolved lithium polysulfides. Dual functionalities such as strong chemical adsorption stability and high conductivity are highly desired for an ideal host material for a sulfur-based cathode. Polypyrrole (PPy), as a conductive polymer, was widely studied as matrixes for sulfur cathode due to its high conductivity and strong chemical interaction with soluble polysulfides. Thus, a novel cathode structure consisting of a free-standing sulfur-polypyrrole cathode and a polypyrrole coated separator was designed for flexible Li-S batteries. The PPy materials show strong interaction with dissoluble polysulfides, which could suppress the shuttle effect and improve the cycling stability. In addition, the synthesized PPy film with a rough surface acts as a current collector, which improves the adhesion of sulfur materials and restrain the volume expansion, enhancing the structural stability during the cycling process. For further enhancing the cycling stability, a PPy coated separator was also applied, which could make polysulfides into the cathode side to alleviate the shuttle effect. Moreover, the PPy layer coated on commercial separator is much lighter than other reported interlayers. A soft-packaged flexible Li-S battery has been designed and fabricated for testing the practical application of the designed cathode and separator, which could power a device consisting of 24 light-emitting diode (LED) lights. Moreover, the soft-packaged flexible battery can still show relatively stable cycling performance after repeated bending, indicating the potential application in flexible batteries. A novel vapor phase deposition method was also applied to prepare uniform polypyrrole layer coated sulfur/graphene aerogel composite. The polypyrrole layer simultaneously acts as host and adsorbent for efficient suppression of polysulfides dissolution through strong chemical interaction. The density functional theory (DFT) calculations reveal that the polypyrrole could trap lithium polysulfides through stronger bonding energy. In addition, the deflation of sulfur/graphene hydrogel during the vapor phase deposition process enhances the contact of sulfur with matrixes, resulting in high sulfur utilization and good rate capability. As a result, the synthesized polypyrrole coated sulfur/graphene aerogel composite delivers a specific discharge capacity of 1167 mAh g⁻¹ and 409.1 mAh g⁻¹ at 0.2 C and 5 C respectively. The capacity can maintain at 698 mAh g⁻¹ at 0.5 C after 500 cycles, showing an ultra-slow decay rate of 0.03% per cycle.Keywords: polypyrrole, strong chemical interaction, long-term stability, Li-S batteries
Procedia PDF Downloads 13545 Carbon Nanofibers as the Favorite Conducting Additive for Mn₃O₄ Catalysts for Oxygen Reactions in Rechargeable Zinc-Air Battery
Authors: Augustus K. Lebechi, Kenneth I. Ozoemena
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Rechargeable zinc-air batteries (RZABs) have been described as one of the most viable next-generation ‘beyond-the-lithium-ion’ battery technologies with great potential for renewable energy storage. It is safe, with a high specific energy density (1086 Wh/kg), environmentally benign, and low-cost, especially in resource-limited African countries. For widespread commercialization, the sluggish oxygen reaction kinetics pose a major challenge that impedes the reversibility of the system. Hence, there is a need for low-cost and highly active bifunctional electrocatalysts. Manganese oxide catalysts on carbon conducting additives remain the best couple for the realization of such low-cost RZABs. In this work, hausmannite Mn₃O₄ nanoparticles were synthesized through the annealing method from commercial electrolytic manganese dioxide (EMD), multi-walled carbon nanotubes (MWCNTs) were synthesized via the chemical vapor deposition (CVD) method and carbon nanofibers (CNFs) were synthesized via the electrospinning process with subsequent carbonization. Both Mn₃O₄ catalysts and the carbon conducting additives (MWCNT and CNF) were thoroughly characterized using X-ray powder diffraction spectroscopy (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Composite electrocatalysts (Mn₃O₄/CNT and Mn₃O₄/CNF) were investigated for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an alkaline medium. Using the established electrocatalytic modalities for evaluating the electrocatalytic performance of materials (including double layer, electrochemical active surface area, roughness factor, specific current density, and catalytic stability), CNFs proved to be the most efficient conducting additive material for the Mn₃O₄ catalyst. From the DFT calculations, the higher performance of the CNFs over the MWCNTs is related to the ability of the CNFs to allow for a more favorable distribution of the d-electrons of the manganese (Mn) and enhanced synergistic effect with Mn₃O₄ for weaker adsorption energies of the oxygen intermediates (O*, OH* and OOH*). In a proof-of-concept, Mn₃O₄/CNF was investigated as the air cathode for rechargeable zinc-air battery (RZAB) in a micro-3D-printed cell configuration. The RZAB showed good performance in terms of open circuit voltage (1.77 V), maximum power density (177.5 mW cm-2), areal-discharge energy and cycling stability comparable to Pt/C (20 wt%) + IrO2. The findings here provide fresh physicochemical perspectives on the future design and utility of CNFs for developing manganese-based RZABs.Keywords: bifunctional electrocatalyst, oxygen evolution reaction, oxygen reduction reactions, rechargeable zinc-air batteries.
Procedia PDF Downloads 5344 Blue Hydrogen Production Via Catalytic Aquathermolysis Coupled with Direct Carbon Dioxide Capture Via Adsorption
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
Procedia PDF Downloads 2143 Efficiency of Different Types of Addition onto the Hydration Kinetics of Portland Cement
Authors: Marine Regnier, Pascal Bost, Matthieu Horgnies
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Some of the problems to be solved for the concrete industry are linked to the use of low-reactivity cement, the hardening of concrete under cold-weather and the manufacture of pre-casted concrete without costly heating step. The development of these applications needs to accelerate the hydration kinetics, in order to decrease the setting time and to obtain significant compressive strengths as soon as possible. The mechanisms enhancing the hydration kinetics of alite or Portland cement (e.g. the creation of nucleation sites) were already studied in literature (e.g. by using distinct additions such as titanium dioxide nanoparticles, calcium carbonate fillers, water-soluble polymers, C-S-H, etc.). However, the goal of this study was to establish a clear ranking of the efficiency of several types of additions by using a robust and reproducible methodology based on isothermal calorimetry (performed at 20°C). The cement was a CEM I 52.5N PM-ES (Blaine fineness of 455 m²/kg). To ensure the reproducibility of the experiments and avoid any decrease of the reactivity before use, the cement was stored in waterproof and sealed bags to avoid any contact with moisture and carbon dioxide. The experiments were performed on Portland cement pastes by using a water-to-cement ratio of 0.45, and incorporating different compounds (industrially available or laboratory-synthesized) that were selected according to their main composition and their specific surface area (SSA, calculated using the Brunauer-Emmett-Teller (BET) model and nitrogen adsorption isotherms performed at 77K). The intrinsic effects of (i) dry powders (e.g. fumed silica, activated charcoal, nano-precipitates of calcium carbonate, afwillite germs, nanoparticles of iron and iron oxides , etc.), and (ii) aqueous solutions (e.g. containing calcium chloride, hydrated Portland cement or Master X-SEED 100, etc.) were investigated. The influence of the amount of addition, calculated relatively to the dry extract of each addition compared to cement (and by conserving the same water-to-cement ratio) was also studied. The results demonstrated that the X-SEED®, the hydrated calcium nitrate, the calcium chloride (and, at a minor level, a solution of hydrated Portland cement) were able to accelerate the hydration kinetics of Portland cement, even at low concentration (e.g. 1%wt. of dry extract compared to cement). By using higher rates of additions, the fumed silica, the precipitated calcium carbonate and the titanium dioxide can also accelerate the hydration. In the case of the nano-precipitates of calcium carbonate, a correlation was established between the SSA and the accelerating effect. On the contrary, the nanoparticles of iron or iron oxides, the activated charcoal and the dried crystallised hydrates did not show any accelerating effect. Future experiments will be scheduled to establish the ranking of these additions, in terms of accelerating effect, by using low-reactivity cements and other water to cement ratios.Keywords: acceleration, hydration kinetics, isothermal calorimetry, Portland cement
Procedia PDF Downloads 25042 CsPbBr₃@MOF-5-Based Single Drop Microextraction for in-situ Fluorescence Colorimetric Detection of Dechlorination Reaction
Authors: Yanxue Shang, Jingbin Zeng
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Chlorobenzene homologues (CBHs) are a category of environmental pollutants that can not be ignored. They can stay in the environment for a long period and are potentially carcinogenic. The traditional degradation method of CBHs is dechlorination followed by sample preparation and analysis. This is not only time-consuming and laborious, but the detection and analysis processes are used in conjunction with large-scale instruments. Therefore, this can not achieve rapid and low-cost detection. Compared with traditional sensing methods, colorimetric sensing is simpler and more convenient. In recent years, chromaticity sensors based on fluorescence have attracted more and more attention. Compared with sensing methods based on changes in fluorescence intensity, changes in color gradients are easier to recognize by the naked eye. Accordingly, this work proposes to use single drop microextraction (SDME) technology to solve the above problems. After the dechlorination reaction was completed, the organic droplet extracts Cl⁻ and realizes fluorescence colorimetric sensing at the same time. This method was integrated sample processing and visual in-situ detection, simplifying the detection process. As a fluorescence colorimetric sensor material, CsPbBr₃ was encapsulated in MOF-5 to construct CsPbBr₃@MOF-5 fluorescence colorimetric composite. Then the fluorescence colorimetric sensor was constructed by dispersing the composite in SDME organic droplets. When the Br⁻ in CsPbBr₃ exchanges with Cl⁻ produced by the dechlorination reactions, it is converted into CsPbCl₃. The fluorescence color of the single droplet of SDME will change from green to blue emission, thereby realizing visual observation. Therein, SDME can enhance the concentration and enrichment of Cl⁻ and instead of sample pretreatment. The fluorescence color change of CsPbBr₃@MOF-5 can replace the detection process of large-scale instruments to achieve real-time rapid detection. Due to the absorption ability of MOF-5, it can not only improve the stability of CsPbBr₃, but induce the adsorption of Cl⁻. Simultaneously, accelerate the exchange of Br- and Cl⁻ in CsPbBr₃ and the detection process of Cl⁻. The absorption process was verified by density functional theory (DFT) calculations. This method exhibits exceptional linearity for Cl⁻ in the range of 10⁻² - 10⁻⁶ M (10000 μM - 1 μM) with a limit of detection of 10⁻⁷ M. Whereafter, the dechlorination reactions of different kinds of CBHs were also carried out with this method, and all had satisfactory detection ability. Also verified the accuracy by gas chromatography (GC), and it was found that the SDME we developed in this work had high credibility. In summary, the in-situ visualization method of dechlorination reaction detection was a combination of sample processing and fluorescence colorimetric sensing. Thus, the strategy researched herein represents a promising method for the visual detection of dechlorination reactions and can be extended for applications in environments, chemical industries, and foods.Keywords: chlorobenzene homologues, colorimetric sensor, metal halide perovskite, metal-organic frameworks, single drop microextraction
Procedia PDF Downloads 13741 Towards the Rapid Synthesis of High-Quality Monolayer Continuous Film of Graphene on High Surface Free Energy Existing Plasma Modified Cu Foil
Authors: Maddumage Don Sandeepa Lakshad Wimalananda, Jae-Kwan Kim, Ji-Myon Lee
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Graphene is an extraordinary 2D material that shows superior electrical, optical, and mechanical properties for the applications such as transparent contacts. Further, chemical vapor deposition (CVD) technique facilitates to synthesizing of large-area graphene, including transferability. The abstract is describing the use of high surface free energy (SFE) and nano-scale high-density surface kinks (rough) existing Cu foil for CVD graphene growth, which is an opposite approach to modern use of catalytic surfaces for high-quality graphene growth, but the controllable rough morphological nature opens new era to fast synthesis (less than the 50s with a short annealing process) of graphene as a continuous film over conventional longer process (30 min growth). The experiments were shown that high SFE condition and surface kinks on Cu(100) crystal plane existing Cu catalytic surface facilitated to synthesize graphene with high monolayer and continuous nature because it can influence the adsorption of C species with high concentration and which can be facilitated by faster nucleation and growth of graphene. The fast nucleation and growth are lowering the diffusion of C atoms to Cu-graphene interface, which is resulting in no or negligible formation of bilayer patches. High energy (500W) Ar plasma treatment (inductively Coupled plasma) was facilitated to form rough and high SFE existing (54.92 mJm-2) Cu foil. This surface was used to grow the graphene by using CVD technique at 1000C for 50s. The introduced kink-like high SFE existing point on Cu(100) crystal plane facilitated to faster nucleation of graphene with a high monolayer ratio (I2D/IG is 2.42) compared to another different kind of smooth morphological and low SFE existing Cu surfaces such as Smoother surface, which is prepared by the redeposit of Cu evaporating atoms during the annealing (RRMS is 13.3nm). Even high SFE condition was favorable to synthesize graphene with monolayer and continuous nature; It fails to maintain clean (surface contains amorphous C clusters) and defect-free condition (ID/IG is 0.46) because of high SFE of Cu foil at the graphene growth stage. A post annealing process was used to heal and overcome previously mentioned problems. Different CVD atmospheres such as CH4 and H2 were used, and it was observed that there is a negligible change in graphene nature (number of layers and continuous condition) but it was observed that there is a significant difference in graphene quality because the ID/IG ratio of the graphene was reduced to 0.21 after the post-annealing with H2 gas. Addition to the change of graphene defectiveness the FE-SEM images show there was a reduction of C cluster contamination of the surface. High SFE conditions are favorable to form graphene as a monolayer and continuous film, but it fails to provide defect-free graphene. Further, plasma modified high SFE existing surface can be used to synthesize graphene within 50s, and a post annealing process can be used to reduce the defectiveness.Keywords: chemical vapor deposition, graphene, morphology, plasma, surface free energy
Procedia PDF Downloads 24040 Carboxyfullerene-Modified Titanium Dioxide Nanoparticles in Singlet Oxygen and Hydroxyl Radicals Scavenging Activity
Authors: Kai-Cheng Yang, Yen-Ling Chen, Er-Chieh Cho, Kuen-Chan Lee
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Titanium dioxide nanomaterials offer superior protection for human skin against the full spectrum of ultraviolet light. However, some literature reviews indicated that it might be associated with adverse effects such as cytotoxicity or reactive oxygen species (ROS) due to their nanoscale. The surface of fullerene is covered with π electrons constituting aromatic structures, which can effectively scavenge large amount of radicals. Unfortunately, fullerenes are poor solubility in water, severe aggregation, and toxicity in biological applications when dispersed in solvent have imposed the limitations to the use of fullerenes. Carboxyfullerene acts as the scavenger of radicals for several years. Some reports indicate that carboxyfullerene not only decrease the concentration of free radicals in ambience but also prevent cells from reducing the number or apoptosis under UV irradiation. The aim of this study is to decorate fullerene –C70-carboxylic acid (C70-COOH) on the surface of titanium dioxide nanoparticles (P25) for the purpose of scavenging ROS during the irradiation. The modified material is prepared through the esterification of C70-COOH with P25 (P25/C70-COOH). The binding edge and structure are studied by using Transmission electron microscope (TEM) and Fourier transform infrared (FTIR). The diameter of P25 is about 30 nm and C70-COOH is found to be conjugated on the edge of P25 in aggregation morphology with the size of ca. 100 nm. In the next step, the FTIR was used to confirm the binding structure between P25 and C70-COOH. There are two new peaks are shown at 1427 and 1720 cm-1 for P25/C70-COOH, resulting from the C–C stretch and C=O stretch formed during esterification with dilute sulfuric acid. The IR results further confirm the chemically bonded interaction between C70-COOH and P25. In order to provide the evidence of scavenging radical ability of P25/C70-COOH, we chose pyridoxine (Vit.B6) and terephthalic acid (TA) to react with singlet oxygen and hydroxyl radicals. We utilized these chemicals to observe the radicals scavenging statement via detecting the intensity of ultraviolet adsorption or fluorescence emission. The UV spectra are measured by using different concentration of C70-COOH modified P25 with 1mM pyridoxine under UV irradiation for various duration times. The results revealed that the concentration of pyridoxine was increased when cooperating with P25/C70-COOH after three hours as compared with control (only P25). It indicates fewer radicals could be reacted with pyridoxine because of the absorption via P25/C70-COOH. The fluorescence spectra are observed by measuring P25/C70-COOH with 1mM terephthalic acid under UV irradiation for various duration times. The fluorescence intensity of TAOH was decreased in ten minutes when cooperating with P25/C70-COOH. Here, it was found that the fluorescence intensity was increased after thirty minutes, which could be attributed to the saturation of C70-COOH in the absorption of radicals. However, the results showed that the modified P25/C70-COOH could reduce the radicals in the environment. Therefore, we expect that P25/C70-COOH is a potential materials in using for antioxidant.Keywords: titanium dioxide, fullerene, radical scavenging activity, antioxidant
Procedia PDF Downloads 39839 Improvement of Activity of β-galactosidase from Kluyveromyces lactis via Immobilization on Polyethylenimine-Chitosan
Authors: Carlos A. C. G. Neto, Natan C. G. e Silva , Thaís de O. Costa, Luciana R. B. Gonçalves, Maria V. P. Rocha
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β-galactosidases (E.C. 3.2.1.23) are enzymes that have attracted by catalyzing the hydrolysis of lactose and in producing galacto-oligosaccharides by favoring transgalactosylation reactions. These enzymes, when immobilized, can have some enzymatic characteristics substantially improved, and the coating of supports with multifunctional polymers is a promising alternative to enhance the stability of the biocatalysts, among which polyethylenimine (PEI) stands out. PEI has certain properties, such as being a flexible polymer that suits the structure of the enzyme, giving greater stability, especially for multimeric enzymes such as β-galactosidases. Besides that, protects them from environmental variations. The use of chitosan support coated with PEI could improve the catalytic efficiency of β-galactosidase from Kluyveromyces lactis in the transgalactosylation reaction for the production of prebiotics, such as lactulose since this strain is more effective in the hydrolysis reaction. In this context, the aim of the present work was first to develop biocatalysts of β-galactosidase from K. lactis immobilized on chitosan-coated with PEI, determining the immobilization parameters, its operational and thermal stability, and then to apply it in hydrolysis and transgalactolisation reactions to produce lactulose using whey as a substrate. The immobilization of β-galactosidase in chitosan previously functionalized with 0.8% (v/v) glutaraldehyde and then coated with 10% (w/v) PEI solution was evaluated using an enzymatic load of 10 mg protein per gram support. Subsequently, the hydrolysis and transgalactosylation reactions were conducted at 50 °C, 120 RPM for 20 minutes, using whey supplemented with fructose at a ratio of 1:2 lactose/fructose, totaling 200 g/L. Operational stability studies were performed in the same conditions for 10 cycles. Thermal stabilities of biocatalysts were conducted at 50 ºC in 50 mM phosphate buffer, pH 6.6 with 0.1 mM MnCl2. The biocatalyst whose support was coated was named CHI_GLU_PEI_GAL, and the one that was not coated was named CHI_GLU_GAL. The coating of the support with PEI considerably improved the parameters of immobilization. The immobilization yield increased from 56.53% to 97.45%, biocatalyst activity from 38.93 U/g to 95.26 U/g and the efficiency from 3.51% to 6.0% for uncoated and coated support, respectively. The biocatalyst CHI_GLU_PEI_GAL was better than CHI_GLU_GAL in the hydrolysis of lactose and production of lactulose, converting 97.05% of lactose at 5 min of reaction and producing 7.60 g/L lactulose in the same time interval. QUI_GLU_PEI_GAL biocatalyst was stable in the hydrolysis reactions of lactose during the 10 cycles evaluated, converting 73.45% lactose even after the tenth cycle, and in the lactulose production was stable until the fifth cycle evaluated, producing 10.95 g/L lactulose. However, the thermal stability of CHI_GLU_GAL biocatalyst was superior, with a half-life time 6 times higher, probably because the enzyme was immobilized by covalent bonding, which is stronger than adsorption (CHI_GLU_PEI_GAL). Therefore, the strategy of coating the supports with PEI has proven to be effective for the immobilization of β-galactosidase from K. lactis, considerably improving the immobilization parameters, as well as, the catalytic action of the enzyme. Besides that, this process can be economically viable due to the use of an industrial residue as a substrate.Keywords: β-galactosidase, immobilization, kluyveromyces lactis, lactulose, polyethylenimine, transgalactosylation reaction, whey
Procedia PDF Downloads 10838 Recirculation Type Photocatalytic Reactor for Degradation of Monocrotophos Using TiO₂ and W-TiO₂ Coated Immobilized Clay Beads
Authors: Abhishek Sraw, Amit Sobti, Yamini Pandey, R. K. Wanchoo, Amrit Pal Toor
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Monocrotophos (MCP) is a widely used pesticide in India, which belong to an extremely toxic organophosphorus family, is persistent in nature and its toxicity is widely reported in all environmental segments in the country. Advanced Oxidation Process (AOP) is a promising solution to the problem of water pollution. TiO₂ is being widely used as a photocatalyst because of its many advantages, but it has a large band gap, due to which it is modified using metal and nonmetal dopant to make it active under sunlight and visible light. The use of nanosized powdered catalysts makes the recovery process extremely complicated. Hence the aim is to use low cost, easily available, eco-friendly clay material in form of bead as the support for the immobilization of catalyst, to solve the problem of post-separation of suspended catalyst from treated water. A recirculation type photocatalytic reactor (RTPR), using ultraviolet light emitting source (blue black lamp) was designed which work effectively for both suspended catalysts and catalyst coated clay beads. The bare, TiO₂ and W-TiO₂ coated clay beads were characterized by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS) and N₂ adsorption–desorption measurements techniques (BET) for their structural, textural and electronic properties. The study involved variation of different parameters like light conditions, recirculation rate, light intensity and initial MCP concentration under UV and sunlight for the degradation of MCP. The degradation and mineralization studies of the insecticide solution were performed using UV-Visible spectrophotometer, and COD vario-photometer and GC-MS analysis respectively. The main focus of the work lies in checking the recyclability of the immobilized TiO₂ over clay beads in the developed RTPR up to 30 continuous cycles without reactivation of catalyst. The results demonstrated the economic feasibility of the utilization of developed RTPR for the efficient purification of pesticide polluted water. The prepared TiO₂ clay beads delivered 75.78% degradation of MCP under UV light with negligible catalyst loss. Application of W-TiO₂ coated clay beads filled RTPR for the degradation of MCP under sunlight, however, shows 32% higher degradation of MCP than the same system based on undoped TiO₂. The COD measurements of TiO₂ coated beads led to 73.75% COD reduction while W-TiO₂ resulted in 87.89% COD reduction. The GC-MS analysis confirms the efficient breakdown of complex MCP molecules into simpler hydrocarbons. This supports the promising application of clay beads as a support for the photocatalyst and proves its eco-friendly nature, excellent recyclability, catalyst holding capacity, and economic viability.Keywords: immobilized clay beads, monocrotophos, recirculation type photocatalytic reactor, TiO₂
Procedia PDF Downloads 17337 Distribution and Ecological Risk Assessment of Trace Elements in Sediments along the Ganges River Estuary, India
Authors: Priyanka Mondal, Santosh K. Sarkar
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The present study investigated the spatiotemporal distribution and ecological risk assessment of trace elements of surface sediments (top 0 - 5 cm; grain size ≤ 0.63 µm) in relevance to sediment quality characteristics along the Ganges River Estuary, India. Sediment samples were collected during ebb tide from intertidal regions covering seven sampling sites of diverse environmental stresses. The elements were analyzed with the help of ICPAES. This positive, mixohaline, macro-tidal estuary has global significance contributing ecological and economic services. Presence of fine-clayey particle (47.03%) enhances the adsorption as well as transportation of trace elements. There is a remarkable inter-metallic variation (mg kg-1 dry weight) in the distribution pattern in the following manner: Al (31801± 15943) > Fe (23337± 7584) > Mn (461±147) > S(381±235) > Zn(54 ±18) > V(43 ±14) > Cr(39 ±15) > As (34±15) > Cu(27 ±11) > Ni (24 ±9) > Se (17 ±8) > Co(11 ±3) > Mo(10 ± 2) > Hg(0.02 ±0.01). An overall trend of enrichment of majority of trace elements was very much pronounced at the site Lot 8, ~ 35km upstream of the estuarine mouth. In contrast, the minimum concentration was recorded at site Gangasagar, mouth of the estuary, with high energy profile. The prevalent variations in trace element distribution are being liable for a set of cumulative factors such as hydrodynamic conditions, sediment dispersion pattern and textural variations as well as non-homogenous input of contaminants from point and non-point sources. In order to gain insight into the trace elements distribution, accumulation, and their pollution status, geoaccumulation index (Igeo) and enrichment factor (EF) were used. The Igeo indicated that surface sediments were moderately polluted with As (0.60) and Mo (1.30) and strongly contaminated with Se (4.0). The EF indicated severe pollution of Se (53.82) and significant pollution of As (4.05) and Mo (6.0) and indicated the influx of As, Mo and Se in sediments from anthropogenic sources (such as industrial and municipal sewage, atmospheric deposition, agricultural run-off, etc.). The significant role of the megacity Calcutta in relevance to the untreated sewage discharge, atmospheric inputs and other anthropogenic activities is worthwhile to mention. The ecological risk for different trace elements was evaluated using sediment quality guidelines, effects range low (ERL), and effect range median (ERM). The concentration of As, Cu and Ni at 100%, 43% and 86% of the sampling sites has exceeded the ERL value while none of the element concentration exceeded ERM. The potential ecological risk index values revealed that As at 14.3% of the sampling sites would pose relatively moderate risk to benthic organisms. The effective role of finer clay particles for trace element distribution was revealed by multivariate analysis. The authors strongly recommend regular monitoring emphasizing on accurate appraisal of the potential risk of trace elements for effective and sustainable management of this estuarine environment.Keywords: pollution assessment, sediment contamination, sediment quality, trace elements
Procedia PDF Downloads 25436 Hygro-Thermal Modelling of Timber Decks
Authors: Stefania Fortino, Petr Hradil, Timo Avikainen
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Timber bridges have an excellent environmental performance, are economical, relatively easy to build and can have a long service life. However, the durability of these bridges is the main problem because of their exposure to outdoor climate conditions. The moisture content accumulated in wood for long periods, in combination with certain temperatures, may cause conditions suitable for timber decay. In addition, moisture content variations affect the structural integrity, serviceability and loading capacity of timber bridges. Therefore, the monitoring of the moisture content in wood is important for the durability of the material but also for the whole superstructure. The measurements obtained by the usual sensor-based techniques provide hygro-thermal data only in specific locations of the wood components. In this context, the monitoring can be assisted by numerical modelling to get more information on the hygro-thermal response of the bridges. This work presents a hygro-thermal model based on a multi-phase moisture transport theory to predict the distribution of moisture content, relative humidity and temperature in wood. Below the fibre saturation point, the multi-phase theory simulates three phenomena in cellular wood during moisture transfer, i.e., the diffusion of water vapour in the pores, the sorption of bound water and the diffusion of bound water in the cell walls. In the multi-phase model, the two water phases are separated, and the coupling between them is defined through a sorption rate. Furthermore, an average between the temperature-dependent adsorption and desorption isotherms is used. In previous works by some of the authors, this approach was found very suitable to study the moisture transport in uncoated and coated stress-laminated timber decks. Compared to previous works, the hygro-thermal fluxes on the external surfaces include the influence of the absorbed solar radiation during the time and consequently, the temperatures on the surfaces exposed to the sun are higher. This affects the whole hygro-thermal response of the timber component. The multi-phase model, implemented in a user subroutine of Abaqus FEM code, provides the distribution of the moisture content, the temperature and the relative humidity in a volume of the timber deck. As a case study, the hygro-thermal data in wood are collected from the ongoing monitoring of the stress-laminated timber deck of Tapiola Bridge in Finland, based on integrated humidity-temperature sensors and the numerical results are found in good agreement with the measurements. The proposed model, used to assist the monitoring, can contribute to reducing the maintenance costs of bridges, as well as the cost of instrumentation, and increase safety.Keywords: moisture content, multi-phase models, solar radiation, timber decks, FEM
Procedia PDF Downloads 16635 Immobilization of β-Galactosidase from Kluyveromyces Lactis on Polyethylenimine-Agarose for Production of Lactulose
Authors: Carlos A. C. G. Neto, Natan C. G. Silva, Thais O. Costa, Luciana R. B. Goncalves, Maria v. P. Rocha
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Galactosidases are enzymes responsible for catalyzing lactose hydrolysis reactions and also favoring transgalactosylation reactions for the production of prebiotics, among which lactulose stands out. These enzymes, when immobilized, can have some enzymatic characteristics substantially improved, and the coating of supports with multifunctional polymers in immobilization processes is a promising alternative in order to extend the useful life of the biocatalysts, for example, the coating with polyethyleneimine (PEI). PEI is a flexible polymer that suits the structure of the enzyme, giving greater stability, especially for multimeric enzymes such as β-galactosidases and also protects it from environmental variations, for example, pH and temperature. In addition, it can substantially improve the immobilization parameters and also the efficiency of enzymatic reactions. In this context, the aim of the present work was first to develop biocatalysts of β-galactosidase from Kluyveromyces lactis immobilized on PEI coated agarose, determining the immobilization parameters, its operational and thermal stability, and then to apply it in the hydrolysis of lactose and synthesis of lactulose, using whey as a substrate. This immobilization strategy was chosen in order to improve the catalytic efficiency of the enzyme in the transgalactosylation reaction for the production of prebiotics, and there are few studies with β-galactosidase from this strain. The immobilization of β-galactosidase in agarose previously functionalized with 48% (w/v) glycidol and then coated with 10% (w/v) PEI solution was evaluated using an enzymatic load of 10 mg/g of protein. Subsequently, the hydrolysis and transgalactosylation reactions were conducted at 50 °C, 120 RPM for 20 minutes, using whey (66.7 g/L of lactose) supplemented with 133.3 g/L fructose at a ratio of 1:2 (lactose/fructose). Operational stability studies were performed in the same conditions for 10 cycles. Thermal stabilities of biocatalysts were conducted at 50 ºC in 50 mM phosphate buffer, pH 6.6, with 0.1 mM MnCl2. The biocatalysts whose supports were coated were named AGA_GLY_PEI_GAL, and those that were not coated were named AGA_GLY_GAL. The coating of the support with PEI considerably improved immobilization yield (2.6-fold), the biocatalyst activity (1.4-fold), and efficiency (2.2-fold). The biocatalyst AGA_GLY_PEI_GAL was better than AGA_GLY_GAL in hydrolysis and transgalactosylation reactions, converting 88.92% of lactose at 5 min of reaction and obtaining a residual concentration of 5.24 g/L. Besides that, it was produced 13.90 g/L lactulose in the same time interval. AGA_GLY_PEI_GAL biocatalyst was stable during the 10 cycles evaluated, converting approximately 80% of lactose and producing 10.95 g/L of lactulose even after the tenth cycle. However, the thermal stability of AGA_GLY_GAL biocatalyst was superior, with a half-life time 5 times higher, probably because the enzyme was immobilized by covalent bonding, which is stronger than adsorption (AGA_GLY_PEI_GAL). Therefore, the strategy of coating the supports with PEI has proven to be effective for the immobilization of β-galactosidase from K. lactis, considerably improving the immobilization parameters, as well as the enzyme, catalyzed reactions. In addition, the use of whey as a raw material for lactulose production has proved to be an industrially advantageous alternative.Keywords: β-galactosidase, immobilization, lactulose, polyethylenimine, whey
Procedia PDF Downloads 11334 Implementation of a PDMS Microdevice for the Improved Purification of Circulating MicroRNAs
Authors: G. C. Santini, C. Potrich, L. Lunelli, L. Vanzetti, S. Marasso, M. Cocuzza, C. Pederzolli
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The relevance of circulating miRNAs as non-invasive biomarkers for several pathologies is nowadays undoubtedly clear, as they have been found to have both diagnostic and prognostic value able to add fundamental information to patients’ clinical picture. The availability of these data, however, relies on a time-consuming process spanning from the sample collection and processing to the data analysis. In light of this, strategies which are able to ease this procedure are in high demand and considerable effort have been made in developing Lab-on-a-chip (LOC) devices able to speed up and standardise the bench work. In this context, a very promising polydimethylsiloxane (PDMS)-based microdevice which integrates the processing of the biological sample, i.e. purification of extracellular miRNAs, and reverse transcription was previously developed in our lab. In this study, we aimed at the improvement of the miRNA extraction performances of this micro device by increasing the ability of its surface to absorb extracellular miRNAs from biological samples. For this purpose, we focused on the modulation of two properties of the material: roughness and charge. PDMS surface roughness was modulated by casting with several templates (terminated with silicon oxide coated by a thin anti-adhesion aluminum layer), followed by a panel of curing conditions. Atomic force microscopy (AFM) was employed to estimate changes at the nanometric scale. To introduce modifications in surface charge we functionalized PDMS with different mixes of positively charged 3-aminopropyltrimethoxysilanes (APTMS) and neutral poly(ethylene glycol) silane (PEG). The surface chemical composition was characterized by X-ray photoelectron spectroscopy (XPS) and the number of exposed primary amines was quantified with the reagent sulfosuccinimidyl-4-o-(4,4-dimethoxytrityl) butyrate (s-SDTB). As our final end point, the adsorption rate of all these different conditions was assessed by fluorescence microscopy by incubating a synthetic fluorescently-labeled miRNA. Our preliminary analysis identified casting on thermally grown silicon oxide, followed by a curing step at 85°C for 1 hour, as the most efficient technique to obtain a PDMS surface roughness in the nanometric scaleable to trap miRNA. In addition, functionalisation with 0.1% APTMS and 0.9% PEG was found to be a necessary step to significantly increase the amount of microRNA adsorbed on the surface, therefore, available for further steps as on-chip reverse transcription. These findings show a substantial improvement in the extraction efficiency of our PDMS microdevice, ultimately leading to an important step forward in the development of an innovative, easy-to-use and integrated system for the direct purification of less abundant circulating microRNAs.Keywords: circulating miRNAs, diagnostics, Lab-on-a-chip, polydimethylsiloxane (PDMS)
Procedia PDF Downloads 31033 Algal/Bacterial Membrane Bioreactor for Bioremediation of Chemical Industrial Wastewater Containing 1,4 Dioxane
Authors: Ahmed Tawfik
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Oxidation of 1,4 dioxane produces metabolites by-products involving glycolaldehyde and acids that have geno- and cytotoxicity impact on microbial degradation. Thereby, the incorporation of algae with bacteria in the treatment system would eliminate and overcome the accumulation of metabolites that are utilized as a carbon source for the build-up of biomass. Therefore, the aim of the present study is to assess the potential of algae/bacteria-based membrane bioreactor (AB-MBR) for biodegradation of 1,4 dioxane-rich wastewater at a high imposed loading rate. Three identical reactors, i.e., AB-MBR1, AB-MBR2, and AB-MBR3, were operated in parallel at 1,4 dioxane loading rates of 641.7, 320.9, and 160.4 mg/L. d., and HRTs of 6.0, 12 and 24 h. respectively. The AB-MBR1 achieved 1,4 dioxane removal rate of 263.7 mg/L.d., where the residual value in the treated effluent amounted to 94.4±22.9 mg/L. Reducing the 1,4 dioxane loading rate (LR) to 320.9 mg/L.d in the AB-MBR2 maximized the removal rate efficiency of 265.9 mg/L.d., with a removal efficiency of 82.8±3.2%. The minimum value of 1,4 dioxane of 17.3±1.8 mg/L in the treated effluent of AB-MBR3 was obtained at an HRT of 24.0 h and loading rate of 160.4 mg/L.d. The mechanism of 1,4 dioxane degradation in AB-MBR was a combination of volatilization (8.03±0.6%), UV oxidation (14.1±0.9%), microbial biodegradation (49.1±3.9%) and absorption/uptake and assimilation by algae (28.8±2.%). Further, the Thioclava, Afipia, and Mycobacterium genera oxidized and produced the required enzymes for hydrolysis and cleavage of the dioxane ring into 2-hydroxy-1,4 dioxane. Moreover, the fungi, i.e., Basidiomycota and Cryptomycota, played a big role in the degradation of the 1,4 dioxane into 2-hydroxy-1,4 dioxane. Xanthobacter and Mesorhizobium were involved in the metabolism process by secreting alcohol dehydrogenase (ADH), aldehyde dehydrogenase (ALDH), and glycolate oxidase. Bacteria and fungi produced dehydrogenase (DH) for the transformation of 2-hydroxy-1,4 dioxane into 2-hydroxy-ethoxyacetaldehyde. The latter is converted into Ethylene glycol by Aldehyde hydrogenase (ALDH). Ethylene glycol is oxidized into acids using Alcohol hydrogenase (ADH). The Diatomea, Chlorophyta, and Streptophyta utilize the metabolites for biomass assimilation and produce the required oxygen for further oxidation of the dioxane and its metabolites by-products of bacteria and fungi. The major portion of metabolites (ethylene glycol, glycolic acid, and oxalic acid were removed due to uptake and absorption by algae (43±4.3%), followed by adsorption (18.4±0.9%). The volatilization and UV oxidation contribution for the degradation of metabolites were 8.7±0.7% and 12.3±0.8%, respectively. The capabilities of genera Defluviimonas, Thioclava, Luteolibacter, and Afipia. The genera of Defluviimonas, Thioclava, Luteolibacter, and Mycobacterium were grown under a high 1,4 dioxane LR of 641.7 mg/L.d. The Chlorophyta (4.1-43.6%), Streptophyta (2.5-21.7%), and Diatomea (0.8-1.4%) phyla were dominant for degradation of 1,4 dioxane. The results of this study strongly demonstrated that the bioremediation and bioaugmentation process can safely remove 1,4 dioxane from industrial wastewater while minimizing environmental concerns and reducing economic costs.Keywords: wastewater, membrane bioreactor, bacterial community, algal community
Procedia PDF Downloads 3932 Precursor Synthesis of Carbon Materials with Different Aggregates Morphologies
Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva
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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide
Procedia PDF Downloads 32731 Catalytic Ammonia Decomposition: Cobalt-Molybdenum Molar Ratio Effect on Hydrogen Production
Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez
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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.Keywords: CEDI, hydrogen carrier, LHHW, RDS
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