Search results for: hydrothermal reactor

Authors: Longkui Zhu, Zhengcao Li

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High temperature gas-cooled reactors (HTGRs) are considered as one of the next-generation advanced nuclear reactors, in which porous nuclear graphite is used as neutron moderators, reflectors, structure materials, and cooled by inert helium. Radioactive tritium and ¹⁴C are generated in terms of reactions of thermal neutrons and ⁶Li, ¹⁴N, ¹⁰B impurely within nuclear graphite and the coolant during HTGRs operation. Currently, hydrogen and nitrogen diffusion behavior together with nuclear graphite microstructure evolution were investigated to minimize the radioactive waste release, using thermogravimetric analysis, X-ray computed tomography, the BET and mercury standard porosimetry methods. It is found that the peak value of graphite weight loss emerged at 573-673 K owing to nitrogen diffusion from graphite pores to outside when the system was subjected to vacuum. Macropore volume became larger while porosity for mesopores was smaller with temperature ranging from ambient temperature to 1073 K, which was primarily induced by coalescence of the subscale pores. It is suggested that the porous nuclear graphite should be first subjected to vacuum at 573-673 K to minimize the nitrogen and the radioactive 14°C before operation in HTGRs. Then, results on hydrogen diffusion show that the diffusible hydrogen and tritium could permeate into the coolant with diffusion coefficients of > 0.5 × 10⁻⁴ cm²·s⁻¹ at 50 bar. As a consequence, the freshly-generated diffusible tritium could release quickly to outside once formed, and an effective approach for minimizing the amount of radioactive tritium is to make the impurity contents extremely low in nuclear graphite and the coolant. Besides, both two- and three-dimensional observations indicate that macro and mesopore volume along with total porosity decreased with temperature at 50 bar on account of synergistic effects of applied compression strain, sharpened pore morphology, and non-uniform temperature distribution.

Keywords: advanced high temperature gas-cooled reactor, hydrogen and nitrogen diffusion, microstructure evolution, nuclear graphite, radioactive waste management

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Authors: N. Stoeva, I. Spassova, R. Nickolov, M. Khristova

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Exhaust gases from stationary and mobile combustion sources contain nitrogen oxides that cause a variety of environmentally harmful effects. The most common approach of their elimination is the catalytic reaction in the exhaust using various reduction agents such as NH3, CO and hydrocarbons. Transition metals (Co, Ni, Cu, etc.) are the most widely used as active components for deposition on various supports. However, since the interaction between different catalyst components have been extensively studied in different types of reaction systems, the possible cooperation between active components and the support material and the underlying mechanisms have not been thoroughly investigated. The support structure may affect how these materials maintain an active phase. The objective is to investigate the addition of carbonaceous materials with different nature and texture characteristics on the properties of the resulting silica-carbon support and how it influences of the catalytic properties of the supported copper and cobalt catalysts for reduction of NO with CO. The versatility of the physico-chemical properties of the composites and the supported copper and cobalt catalysts are discussed with an emphasis on the relationship of the properties with the catalytic performance. The catalysts were prepared by sol-gel process and were characterized by XRD, XPS, AAS and BET analysis. The catalytic experiments were carried out in catalytic flow apparatus with isothermal flow reactor in the temperature range 20–300оС. After the catalytic test temperature-programmed desorption (TPD) was carried out. The transient response method was used to study the interaction of the gas phase with the catalyst surface. The role of the interaction between the support and the active phase on the catalyst’s activity in the studied reaction was discussed. We suppose the carbon particles with small sizes to participate in the formation of the active sites for the reduction of NO with CO along with their effect on the kind of deposited metal oxide phase. The existence of micropore texture for some of composites also influences by mass-transfer limitations.

Keywords: catalysts, no reduction, composites, bet analysis

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Authors: Sheila Shahidi, Hootan Rezaee, Abosaeed Rashidi, Mahmood Ghoranneviss

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Plasma treatment has an explosive increase in interest and use in industrial applications as for example in medical, biomedical, automobile, electronics, semiconductor and textile industry. A lot of intensive basic research has been performed in the last decade in the field of textiles along with technical textiles. Textile manufacturers and end-users alike have been searching for ways to improve the surface properties of natural and man-made fibers. Specifically, there is a need to improve adhesion and wettability. Functional groups may be introduced onto the fiber surface by using gas plasma treatments, improving fiber surface properties without affecting the fiber’s bulk properties. In this research work, ZnO nanoparticles (ZnO-NPs) were insitue synthesized by sonochemical method at room temperature on both untreated and plasma pretreated cotton woven fabric. Oxygen and nitrogen plasmas were used for pre-functionalization of cotton fabric. And the effect of oxygen and nitrogen pre-functionalization on adhesion properties between ZnO nanoparticles and cotton surface were studied. The results show that nanoparticles with average sizes of 20-100 nm with different morphologies have been created on the surface of samples. Synthesis of ZnO-NPs was varied in the morphological transformation by changes in zinc acetate dehydrate concentration. Characterizations were carried out using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Inductive coupled plasma (ICP) and Spectrophotometery. The antibacterial activities of the fabrics were assessed semi-quantitatively by the colonies count method. The results show that the finished fabric demonstrated significant antibacterial activity against S. aureus in antibacterial test. The wash fastness of both untreated and plasma pretreated samples after 30 times of washing was investigated. The results showed that the parameters of plasma reactor plays very important role for improving the antibacterial durability.

Keywords: antibacterial activity, cotton, fabric, nanoparticles, plasma

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Authors: Miguel A. Jimenez Barros, Elyn L. Solano Charris, Luis E. Ramirez, Lauren Castro Bolano, Carlos Torres Barreto, Juliana Morales Cubillo

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This project sought to mitigate the high levels of water consumption in industrial processes in accordance with the water-rationing plan promoted at national and international level due to the water consumption projections published by the United Nations. Water consumption has three main uses, municipal (common use), agricultural and industrial where the latter consumes a minimum percentage (around 20% of the total consumption). Awareness on world water scarcity, a Colombian company responsible for generation of massive consumption products, decided to implement politics and techniques for water treatment, recycling, and reuse. The project consisted in a business technology program that permits a better use of wastewater caused by production operations. This approach reduces the potable water consumption, generates better conditions of water in the sewage dumps, generates a positive environmental impact for the region, and is a reference model in national and international levels. In order to achieve the objective, a process flow diagram was used in order to define the industrial processes that required potable water. This strategy allowed the industry to determine a water reuse plan at the operational level without affecting the requirements associated with the manufacturing process and even more, to support the activities developed in administrative buildings. Afterwards, the company made an evaluation and selection of the chemical and biological processes required for water reuse, in compliance with the Colombian Law. The implementation of the business technology program optimized the water use and recirculation rate up to 70%, accomplishing an important reduction of the regional environmental impact.

Keywords: bio-reactor, potable water, reverse osmosis, water treatment

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Authors: Wala Abou Saoud, Aymen Amine Assadi, Monia Guiza, Abdelkrim Bouzaza, Wael Aboussaoud, Abdelmottaleb Ouederni, Dominique Wolbert

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Volatile organic compounds (VOCs) constitute one of the most important families of chemicals involved in atmospheric pollution, causing damage to the environment and human health, and need, consequently, to be eliminated. Among the promising technologies, dielectric barrier discharge (DBD) plasma - photocatalysis coupling reveals very interesting prospects in terms of process synergy of compounds mineralization’s, with low energy consumption. In this study, the removal of organic compounds such butyraldehyde (BUTY) and dimethyl disulfide (DMDS) (exhaust gasses from animal quartering centers.) in air mixture using DBD plasma coupled with photocatalysis was tested, in order to determine whether or not synergy effect was present. The removal efficiency of these pollutants, a selectivity of CO₂ and CO, and byproducts formation such as ozone formation were investigated in order to evaluate the performance of the combined process. For this purpose, a series of experiments were carried out in a continuous reactor. Many operating parameters were also investigated such as the specific energy of discharge, the inlet concentration of pollutant and the flowrate. It appears from this study that, the performance of the process has enhanced and a synergetic effect is observed. In fact, we note an enhancement of 10 % on removal efficiency. It is interesting to note that the combined system leads to better CO₂ selectivity than for plasma. Consequently, intermediates by-products have been reduced due to various other species (O•, N, OH•, O₂•-, O₃, NO₂, NOx, etc.). Additionally, the behavior of combining DBD plasma and photocatalysis has shown that the ozone can be easily also decomposed in presence of photocatalyst.

Keywords: combined process, DBD plasma, photocatalysis, pilot scale, synergetic effect, VOCs

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Authors: Ulugbek Azimov, Nearchos Stylianidis, Nobuyuki Kawahara, Eiji Tomita

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A chemical kinetics and computational fluid-dynamics (CFD) analysis was performed to evaluate the combustion of syngas derived from biomass and coke-oven solid feedstock in a micro-pilot ignited supercharged dual-fuel engine under lean conditions. For this analysis, a new reduced syngas chemical kinetics mechanism was constructed and validated by comparing the ignition delay and laminar flame speed data with those obtained from experiments and other detail chemical kinetics mechanisms available in the literature. The reaction sensitivity analysis was conducted for ignition delay at elevated pressures in order to identify important chemical reactions that govern the combustion process. The chemical kinetics of NOx formation was analyzed for H2/CO/CO2/CH4 syngas mixtures by using counter flow burner and premixed laminar flame speed reactor models. The new mechanism showed a very good agreement with experimental measurements and accurately reproduced the effect of pressure, temperature and equivalence ratio on NOx formation. In order to identify the species important for NOx formation, a sensitivity analysis was conducted for pressures 4 bar, 10 bar and 16 bar and preheat temperature 300 K. The results show that the NOx formation is driven mostly by hydrogen based species while other species, such as N2, CO2 and CH4, have also important effects on combustion. Finally, the new mechanism was used in a multidimensional CFD simulation to predict the combustion of syngas in a micro-pilot-ignited supercharged dual-fuel engine and results were compared with experiments. The mechanism showed the closest prediction of the in-cylinder pressure and the rate of heat release (ROHR).

Keywords: syngas, chemical kinetics mechanism, internal combustion engine, NOx formation

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Authors: Sarra Kitanou

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Water recycling and reuse is an effective measure to solve the water stress problem. The sustainable use of water resource has become a national development strategy in Morocco. A key aspect of improving overall sustainability is the potential for direct wastewater effluent reuse. However, the hybrid technology membrane bioreactors (MBR) have been identified as an attractive option for producing high quality and nutrient-rich effluents for wastewater treatment. It is based on complex interactions between biological processes, filtration process and rheological properties of the liquid to be treated. Currently, with the evolution of wastewater treatment projects in Morocco, the MBR technology can be used as a technology treating different types of wastewaters and to produce effluent with suitable quality for reuse. However, the energetic consumption of this process is a great concern, which can limit the development and implementation of this technology. In this investigation, the electric energy consumption of an ultrafiltration membrane bioreactor process in domestic wastewater treatment is evaluated and compared to some MBR installations based on literature review. Energy requirements of the MBR are linked to operational parameters and reactor performance. The analysis of energy consumption shows that the biological aeration and membrane filtration are more energy consuming than the other components listed as feed and recirculation pumps. Biological aeration needs 53% of the overall energetic consumption and the specific energy consumption for membrane filtration is about 25%. However, aeration is a major energy consumer, often exceeding 50% share of total energy consumption. The optimal results obtained on the MBR process (pressure p = 1.15 bar), hydraulic retention time (15 h) showed removal efficiencies up to 90% in terms of organic compounds removal, 100% in terms of suspended solids presence and up to 80% reduction of total nitrogen and total phosphorus. The effluent from this MBR system could be considered as qualified for irrigation reuse, showing its potential application in the future.

Keywords: hybrid process, membrane bioreactor, wastewater treatment, reuse

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Authors: Christine Fräulin, Daniela Schurr, Hamed Shahidi Rad, Gerrit Waters, Günter Rinke, Roland Dittmeyer, Michael Nilles

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The reaction mechanisms of many liquid-phase reactions in organic chemistry have not yet been sufficiently clarified. Process conditions of several hundred degrees celsius and pressures to ten megapascals complicate the sampling and the determination of kinetic data. Space resolved in-situ measurements promises new insights. A non-invasive in-situ measurement technique has the advantages that no sample preparation is necessary, there is no change in sample mixture before analysis and the sampling do no lead to interventions in the flow. Thus, the goal of our research was the development of a contact-free spatially resolved measurement technique for kinetic studies of liquid phase reaction under process conditions. Therefore we used laser Raman spectroscopy combined with an optical transparent microchannel reactor. To show the performance of the system we choose the oxidation of cyclohexane as sample reaction. Cyclohexane oxidation is an economically important process. The products are intermediates for caprolactam and adipic acid, which are starting materials for polyamide 6 and 6.6 production. To maintain high selectivities of 70 to 90 %, the reaction is performed in industry at a low conversion of about six percent. As Raman spectroscopy is usually very selective but not very sensitive the detection of the small product concentration in cyclohexane oxidation is quite challenging. To meet these requirements, an optical experimental setup was optimized to determine the concentrations by laser Raman spectroscopy with respect to good detection sensitivity. With this measurement technique space resolved kinetic studies of uncatalysed and homogeneous catalyzed cyclohexane oxidation were carried out to obtain details about the reaction mechanism.

Keywords: in-situ laser raman spectroscopy, space resolved kinetic measurements, homogeneous catalysis, chemistry

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Authors: Koyar Rane

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Nano- to submicron size particles of narrow particle size distribution of semi-conducting TiO₂, ZnO, NiO, CuO, Fe₂O₃ have been synthesized by novel hydrazine method and tested for their gas sensing, photocatalytic and bactericidal activities and the behavior found to be enhanced when the oxides in the thin film forms, that obtained in a specially built spray pyrolysis reactor. Hydrazine method is novel in the sense, say, the UV absorption edge of the white pigment grade wide band gap (~3.2eV) TiO₂ and ZnO shifted to the visible region turning into yellowish particles, indicating modification occurring the band structure. The absorption in the visible region makes these oxides visible light sensitive photocatalysis in degrading pollutants, especially the organic dyes which otherwise increase the chemical oxygen demand of the drinking water, enabling the process feasible not under the harsh energetic UV radiation regime. The electromagnetic radiations on irradiation produce electron-hole pairs Semiconductor + hν → e⁻ + h⁺ The electron-hole pairs thus produced form Reactive Oxygen Species, ROS, on the surface of the semiconductors, O₂(adsorbed)+e⁻ → O₂• - superoxide ion OH-(surface)+h⁺ →•OH - Hydroxyl radical The ROS attack the organic material and micro-organisms. Our antibacterial studies indicate the metal oxides control the Biological Oxygen Demand (BOD) of drinking water which had beyond the safe level normally found in the municipal supply. Metal oxides in the thin film form show overall enhanced properties and the films are reusable. The results of the photodegradation and antibactericidal studies are discussed. Gas sensing studies too have been done to find the versatility of the multifunctional metal oxides.

Keywords: hydrazine method, visible light sensitive, photo-degradation of dyes, water/airborne pollutant

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Authors: Adilah Shariff, Nurhidayah Mohamed Noor, Alexander Lau, Muhammad Azwan Mohd Ali

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Biomass such as corn and cassava wastes if left to decay will release significant quantities of greenhouse gases (GHG) including carbon dioxide and methane. The biomass wastes can be converted into biochar via thermochemical process such as slow pyrolysis. This approach can reduce the biomass wastes as well as preserve its carbon content. Biochar has the potential to be used as a carbon sequester and soil amendment. The aim of this study is to investigate the characteristics of the corn cob, cassava stem, and cassava rhizome in order to identify their potential as pyrolysis feedstocks for biochar production. This was achieved by using the proximate and elemental analyses as well as calorific value and lignocellulosic determination. The second objective is to investigate the effect of pyrolysis temperature on the biochar produced. A fixed bed slow pyrolysis reactor was used to pyrolyze the corn cob, cassava stem, and cassava rhizome. The pyrolysis temperatures were varied between 400 °C and 600 °C, while the heating rate and the holding time were fixed at 5 °C/min and 1 hour, respectively. Corn cob, cassava stem, and cassava rhizome were found to be suitable feedstocks for pyrolysis process because they contained a high percentage of volatile matter more than 80 mf wt.%. All the three feedstocks contained low nitrogen and sulphur content less than 1 mf wt.%. Therefore, during the pyrolysis process, the feedstocks give off very low rate of GHG such as nitrogen oxides and sulphur oxides. Independent of the types of biomass, the percentage of biochar yield is inversely proportional to the pyrolysis temperature. The highest biochar yield for each studied temperature is from slow pyrolysis of cassava rhizome as the feedstock contained the highest percentage of ash compared to the other two feedstocks. The percentage of fixed carbon in all the biochars increased as the pyrolysis temperature increased. The increment of pyrolysis temperature from 400 °C to 600 °C increased the fixed carbon of corn cob biochar, cassava stem biochar and cassava rhizome biochar by 26.35%, 10.98%, and 6.20% respectively. Irrespective of the pyrolysis temperature, all the biochars produced were found to contain more than 60 mf wt.% fixed carbon content, much higher than its feedstocks.

Keywords: biochar, biomass, cassava wastes, corn cob, pyrolysis

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Sonia Besbes, Mahmoud El Hajem, Habib Ben Aissia, Jean Yves Champagne, Jacques Jay

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In this work, we present a computational study for the characterization of the flow in a rectangular bubble column. To simulate the dynamic characteristics of the flow, a three-dimensional transient numerical simulations based on a coupled discrete phase model (DPM) and Volume of Fluid (VOF) model are performed. Modeling of bubble column reactor is often carried out under the assumption of a flat liquid surface with a degassing boundary condition. However, the dynamic behavior of the top surface surmounting the liquid phase will to some extent influence the meandering oscillations of the bubble plume. Therefore it is important to capture the surface behavior, and the assumption of a flat surface may not be applicable. So, the modeling approach needs to account for a dynamic liquid surface induced by the rising bubble plume. The volume of fluid (VOF) model was applied for the liquid and top gas which both interacts with bubbles implemented with a discrete phase model. This model treats the bubbles as Lagrangian particles and the liquid and the top gas as Eulerian phases with a sharp interface. Two-way coupling between Eulerian phases and Lagrangian bubbles are accounted for in a single set continuous phase momentum equation for the mixture of the two Eulerian phases. The effect of gas flow rate on the dynamic and time-averaged flow properties was studied. The time averaged liquid velocity field predicted from simulations and from our previous PIV measurements shows that the liquid is entrained up flow in the wake of the bubbles and down flow near the walls. The simulated and measured vertical velocity profiles exhibit a reasonable agreement looking at the minimum velocity values near the walls and the maximum values at the column center.

Keywords: bubble column, computational fluid dynamics (CFD), coupled DPM and VOF model, hydrodynamics

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Authors: María del Carmen Recio-Ruiz, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol, Tomás Cordero

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Nowadays, fossil resources are main precursors for fuel production. Due to their contribution to the greenhouse effect and their future depletion, there is a constant search for environmentally friendly feedstock alternatives. Biomass residues constitute an interesting replacement for fossil resources because of their zero net CO₂ emissions. One of the main routes to convert biomass into energy and chemicals is pyrolysis. In this work, conventional pyrolysis of different biomass residues highly available such as almond shells, hemp hurds, olive stones, and Kraft lignin, was studied. In a typical experiment, the biomass was crushed and loaded into a fixed bed reactor under continuous nitrogen flow. The influence of temperature (400-800 ºC) and heating rate (10 and 20 ºC/min) on the pyrolysis yield and composition of the different fractions has been studied. In every case, the mass yields revealed that the solid fraction decreased with temperature, while liquid and gas fractions increased due to depolymerization and cracking reactions at high temperatures. The composition of every pyrolysis fraction was studied in detail. The results showed that the composition of the gas fraction was mainly CO, CO₂ when working at low temperatures, and mostly CH₄ and H₂at high temperatures. The solid fraction developed an incipient microporosity, with narrow micropore volume of 0.21 cm³/g. Regarding the liquid fraction, pyrolysis of almond shell, hemp hurds, and olive stones led mainly to a high content in aliphatic acids and furans, due to the high volatile matter content of these biomass (>74 %wt.), and phenols to a lesser degree, which were formed due to the degradation of lignin at higher temperatures. However, when Kraft lignin was used as bio-oil precursor, the presence of phenols was very prominent, and aliphatic compounds were also detected in a lesser extent.

Keywords: Bio-oil, biomass, conventional pyrolysis, lignocellulosic

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Authors: Mareli Hattingh, I. Jaco Van der Walt, Frans B. Waanders

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A waste-to-energy plasma system was designed by Necsa for commercial use to create electricity from unsorted municipal waste. Fly ash particles must be removed from the syngas stream at operating temperatures of 1000 °C and recycled back into the reactor for complete combustion. A 2D2D high efficiency cyclone separator was chosen for this purpose. During this study, two cyclone design methods were explored: The Classic Empirical Method (smaller cyclone) and the Flow Characteristics Method (larger cyclone). These designs were optimized with regard to efficiency, so as to remove at minimum 90% of the fly ash particles of average size 10 μm by 50 μm. Wood was used as feed source at a concentration of 20 g/m³ syngas. The two designs were then compared at room temperature, using Perspex test units and three feed gases of different densities, namely nitrogen, helium and air. System conditions were imitated by adapting the gas feed velocity and particle load for each gas respectively. Helium, the least dense of the three gases, would simulate higher temperatures, whereas air, the densest gas, simulates a lower temperature. The average cyclone efficiencies ranged between 94.96% and 98.37%, reaching up to 99.89% in individual runs. The lowest efficiency attained was 94.00%. Furthermore, the design of the smaller cyclone proved to be more robust, while the larger cyclone demonstrated a stronger correlation between its separation efficiency and the feed temperatures. The larger cyclone can be assumed to achieve slightly higher efficiencies at elevated temperatures. However, both design methods led to good designs. At room temperature, the difference in efficiency between the two cyclones was almost negligible. At higher temperatures, however, these general tendencies are expected to be amplified so that the difference between the two design methods will become more obvious. Though the design specifications were met for both designs, the smaller cyclone is recommended as default particle separator for the plasma system due to its robust nature.

Keywords: Cyclone, design, plasma, renewable energy, solid separation, waste processing

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Authors: Thomas S. Abia II, Citlali Garcia-Saucedo

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A continuous copper precipitation treatment (CCPT) system was conceived at Intel Chandler Site to serve as a first-of-kind (FOK) facility-scale waste copper (Cu), nickel (Ni), and manganese (Mn) co-precipitation facility. The process was designed to treat highly variable wastewater discharged from a substrate packaging research factory. The paper discusses metals co-precipitation induced by internal changes for manufacturing facilities that lack the capacity for hardware expansion due to real estate restrictions, aggressive schedules, or budgetary constraints. Herein, operating parameters such as pH and oxidation reduction potential (ORP) were examined to analyze the ability of the CCPT System to immobilize various waste metals. Additionally, influential factors such as influent concentrations and retention times were investigated to quantify the environmental variability against system performance. A total of 2,027 samples were analyzed and statistically evaluated to measure the performance of CCPT that was internally retrofitted for Mn abatement to meet environmental regulations. In order to enhance the consistency of the influent, a separate holding tank was cannibalized from another system to collect and slow-feed the segregated Mn wastewater from the factory into CCPT. As a result, the baseline influent Mn decreased from 17.2+18.7 mg¹L^-1 at pre-pilot to 5.15+8.11 mg¹L^-1 post-pilot (70.1% reduction). Likewise, the pre-trial and post-trial average influent Cu values to CCPT were 52.0+54.6 mg¹L^-1 and 33.9+12.7 mg¹L^-1, respectively (34.8% reduction). However, the raw Ni content of 0.97+0.39 mg¹L^-1 at pre-pilot increased to 1.06+0.17 mg¹L^-1 at post-pilot. The average Mn output declined from 10.9+11.7 mg¹L^-1 at pre-pilot to 0.44+1.33 mg¹L^-1 at post-pilot (96.0% reduction) as a result of the pH and ORP operating setpoint changes. In similar fashion, the output Cu quality improved from 1.60+5.38 mg¹L^-1 to 0.55+1.02 mg¹L^-1 (65.6% reduction) while the Ni output sustained a 50% enhancement during the pilot study (0.22+0.19 mg¹L^-1 reduced to 0.11+0.06 mg¹L^-1). pH and ORP were shown to be significantly instrumental to the precipitative versatility of the CCPT System.

Keywords: copper, co-precipitation, industrial wastewater treatment, manganese, optimization, pilot study

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Authors: Aghaei Amirkhizi Navideh, Sadjadi Soodeh Sadat, Moghaddam Banaem Leila, Athari Allaf Mitra, Johari Daha Fariba

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Dendrimers are good candidates for preparing metal nanoparticles because they can structurally and chemically well-defined templates and robust stabilizers. Poly amidoamine (PAMAM) dendrimer-based multifunctional cancer therapeutic conjugates have been designed and synthesized in pharmaceutical industry. In addition, encapsulated nanoparticle surfaces are accessible to substrates so that catalytic reactions can be carried out. For preparation of dendimer-metal nanocomposite, a dendrimer solution containing an average of 55 Yb+3 ions per dendrimer was prepared. Prior to reduction, the pH of this solution was adjusted to 7.5 using NaOH. NaBH4 was used to reduce the dendrimer-encapsulated Yb+3 to the zerovalent metal. The pH of the resulting solution was then adjusted to 3, using HClO4, to decompose excess BH4-. The UV-Vis absorption spectra of the mixture were recorded to ensure the formation of Yb-G5-NH2 complex. High-resolution electron microscopy (HRTEM) and size distribution results provide additional information about dendimer-metal nanocomposite shape, size, and size distribution of the particles. The resulting mixture was irradiated in Tehran Research Reactor 2h and neutron fluxes were 3×1011 n/cm2.Sec and the specific activity was 7MBq. Radiochemical and chemical and radionuclide quality control testes were carried. Gamma Spectroscopy and High-performance Liquid Chromatography HPLC, Thin-Layer Chromatography TLC were recorded. The injection of resulting solution to solid tumor in mice shows that it could be resized the tumor. The studies about solid tumors and nano composites show that ytterbium encapsulated-dendrimer radiopharmaceutical could be introduced as a new therapeutic for the treatment of solid tumors.

Keywords: nano-radio pharmaceutical, ytterbium, PAMAM, dendrimers

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Authors: Shweta Hoyani, Charlie Oommen

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HAN-based liquid propellants are perceived as potential substitute for hydrazine in space propulsion. Storage stability for long service life in orbit is one of the key concerns for HAN-based monopropellants because of its reactivity with metallic and non-metallic impurities which could entrain from the surface of fuel tanks and the tubes. The end result of this reactivity directly affects the handling, performance and storability of the liquid propellant. Gaseous products resulting from the decomposition of the propellant can lead to deleterious pressure build up in storage vessels. The partial loss of an energetic component can change the ignition and the combustion behavior and alter the performance of the thruster. The effect of largely plausible metals- iron, copper, chromium, nickel, manganese, molybdenum, zinc, titanium and cadmium on the thermal decomposition mechanism of HAN has been investigated in this context. Studies involving different concentrations of metal ions and HAN at different preheat temperatures have been carried out. Effect of metal ions on the decomposition behavior of HAN has been studied earlier in the context of use of HAN as gun propellant. However the current investigation pertains to the decomposition mechanism of HAN in the context of use of HAN as monopropellant for space propulsion. Decomposition onset temperature, rate of weight loss, heat of reaction were studied using DTA- TGA and total pressure rise and rate of pressure rise during decomposition were evaluated using an in-house built constant volume batch reactor. Besides, reaction mechanism and product profile were studied using TGA-FTIR setup. Iron and copper displayed the maximum reaction. Initial results indicate that iron and copper shows sensitizing effect at concentrations as low as 50 ppm with 60% HAN solution at 80°C. On the other hand 50 ppm zinc does not display any effect on the thermal decomposition of even 90% HAN solution at 80°C.

Keywords: hydroxylammonium nitrate, monopropellant, reaction mechanism, thermal stability

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Authors: Roberta Pecoraro

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The focus of this work was to investigate the potential toxic effect of titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites on nauplii of microcrustacean Artemia sp. In order to assess the nanocomposite’s toxicity, a short-term test was performed by exposing nauplii to solutions containing TiO₂-rGO. To prepare titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites, a green procedure based on solar photoreduction was proposed; it allows to obtain the photocatalysts by exploiting the photocatalytic properties of titania activated by the solar irradiation in order to avoid the high temperatures and pressures required for the standard hydrothermal synthesis. Powders of TiO₂-rGO supplied by the Department of Chemical Sciences (University of Catania) are indicated as TiO₂-rGO at 1% and TiO₂-rGO at 2%. Starting from a stock solution (1mg rGO-TiO₂/10 ml ASPM water) of each type, we tested four different concentrations (serial dilutions ranging from 10⁻¹ to 10⁻⁴ mg/ml). All the solutions have been sonicated for 12 min prior to use. Artificial seawater (called ASPM water) was prepared to guarantee the hatching of the cysts and to maintain nauplii; the durable cysts used in this study, marketed by JBL (JBL GmbH & Co. KG, Germany), were hydrated with ASPM water to obtain nauplii (instar II-III larvae). The hatching of the cysts was carried out in the laboratory by immersing them in ASPM water inside a 500 ml beaker and keeping them constantly oxygenated thanks to an aerator for the insufflation of microbubble air: after 24-48 hours, the cysts hatched, and the nauplii appeared. The nauplii in the second and third stages of development were collected one-to-one, using stereomicroscopes, and transferred into 96-well microplates where one nauplius per well was added. The wells quickly have been filled with 300 µl of each specific concentration of the solution used, and control samples were incubated only with ASPM water. Replication was performed for each concentration. Finally, the microplates were placed on an orbital shaker, and the tests were read after 24 and 48 hours from inoculating the solutions to assess the endpoint (immobility/death) for the larvae. Nauplii that appeared motionless were counted as dead, and the percentages of mortality were calculated for each treatment. The results showed a low percentage of immobilization both for TiO₂-rGO at 1% and TiO₂-rGO at 2% for all concentrations tested: for TiO₂-rGO at 1% was below 12% after 24h and below 15% after 48h; for TiO₂-rGO at 2% was below 8% after 24h and below 12% after 48h. According to other studies in the literature, the results have not shown mortality nor toxic effects on the development of larvae after exposure to rGO. Finally, it is important to highlight that the TiO₂-rGO catalysts were tested in the solar photodegradation of a toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining a high percentage of degradation; therefore, this alternative approach could be considered a good strategy to obtain performing photocatalysts.

Keywords: Nauplii, photocatalytic properties, reduced GO, short-term toxicity test, titanium dioxide

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Authors: Md. Asif Ullah, M. A. R. Sarkar

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This paper illustrates 2-D and 3-D simulations of sub-channels of a Pressurized Water Reactor (PWR) having hexagonal array of fuel rods. At a steady state, the temperature of outer surface of the cladding of fuel rod is kept about 1200°C. The temperature of this isothermal surface is taken as boundary condition for simulation. Water with temperature of 290°C is given as a coolant inlet to the primary water circuit which is pressurized upto 157 bar. Turbulent flow of pressurized water is used for heat removal. In 2-D model, temperature, velocity, pressure and Nusselt number distributions are simulated in a vertical sectional plane through the sub-channels of a hexagonal fuel rod assembly. Temperature, Nusselt number and Y-component of convective heat flux along a line in this plane near the end of fuel rods are plotted for different Reynold’s number. A comparison between X-component and Y-component of convective heat flux in this vertical plane is analyzed. Hexagonal fuel rod assembly has three types of sub-channels according to geometrical shape whose boundary conditions are different too. In 3-D model, temperature, velocity, pressure, Nusselt number, total heat flux magnitude distributions for all the three sub-channels are studied for a suitable Reynold’s number. A horizontal sectional plane is taken from each of the three sub-channels to study temperature, velocity, pressure, Nusselt number and convective heat flux distribution in it. Greater values of temperature, Nusselt number and Y-component of convective heat flux are found for greater Reynold’s number. X-component of convective heat flux is found to be non-zero near the bottom of fuel rod and zero near the end of fuel rod. This indicates that the convective heat transfer occurs totally along the direction of flow near the outlet. As, length to radius ratio of sub-channels is very high, simulation for a short length of the sub-channels are done for graphical interface advantage. For the simulations, Turbulent Flow (K-Є ) module and Heat Transfer in Fluids (ht) module of COMSOL MULTIPHYSICS 5.0 are used.

Keywords: sub-channels, Reynold’s number, Nusselt number, convective heat transfer

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Authors: Paolo Boscaro, Vasile Hulea, François Fajula, Francis Luck, Anne Galarneau

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TiO2 based monoliths with hierarchical macropores and mesopores have been synthesized following a novel one pot sol-gel synthesis method. Taking advantage of spinodal separation that occurs between titanium isopropoxide and an acidic solution in presence of polyethylene oxide polymer, monoliths with homogeneous interconnected macropres of 3 μm in diameter and mesopores of ca. 6 nm (surface area 150 m2/g) are obtained. Furthermore, these monoliths present some carbon and nitrogen (as shown by XPS and elemental analysis), which considerably reduce titanium oxide energy gap and enable light to be absorbed up to 700 nm wavelength. XRD shows that anatase is the dominant phase with a small amount of brookite. Enhanced light absorption and high porosity of the monoliths are responsible for a remarkable photocatalytic activity. Wastewater treatment has been performed in closed reactor under sunlight using orange G dye as target molecule. Glass reactors guarantee that most of UV radiations (to almost 300 nm) of solar spectrum are excluded. TiO2 nanoparticles P25 (usually used in photocatalysis under UV) and un-doped TiO2 monoliths with similar porosity were used as comparison. C,N-doped TiO2 monolith allowed a complete colorant degradation in less than 1 hour, whereas 10 h are necessary for 40% colorant degradation with P25 and un-doped monolith. Experiment performed in the dark shows that only 3% of molecules have been adsorbed in the C,N-doped TiO2 monolith within 1 hour. The much higher efficiency of C,N-doped TiO2 monolith in comparison to P25 and un-doped monolith, proves that doping TiO2 is an essential issue and that nitrogen and carbon are effective dopants. Monoliths offer multiples advantages in respect to nanometric powders: sample can be easily removed from batch (no needs to filter or to centrifuge). Moreover flow reactions can be set up with cylindrical or flat monoliths by simple sheathing or by locking them with O-rings.

Keywords: C-N doped, sunlight photocatalytic activity, TiO2 monolith, visible absorbance

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Authors: Prateek Goyal, Archini Paruthi, Superb K. Misra

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Contamination of water resources has been a major concern, which has drawn attention to the need to develop new material models for treatment of effluents. Existing conventional waste water treatment methods remain ineffective sometimes and uneconomical in terms of remediating contaminants like heavy metal ions (mercury, arsenic, lead, cadmium and chromium); organic matter (dyes, chlorinated solvents) and high salt concentration, which makes water unfit for consumption. We believe that nanotechnology based strategy, where we use nanoparticles as a tool to remediate a class of pollutants would prove to be effective due to its property of high surface area to volume ratio, higher selectivity, sensitivity and affinity. In recent years, scientific advancement has been made to study the application of photocatalytic (ZnO, TiO2 etc.) nanomaterials and magnetic nanomaterials in remediating contaminants (like heavy metals and organic dyes) from water/wastewater. Our study focuses on the synthesis and monitoring remediation efficiency of ZnO, Fe3O4 and Fe3O4 coated ZnO nanoparticulate system for the removal of heavy metals and dyes simultaneously. Multitude of ZnO nanostructures (spheres, rods and flowers) using multiple routes (microwave & hydrothermal approach) offers a wide range of light active photo catalytic property. The phase purity, morphology, size distribution, zeta potential, surface area and porosity in addition to the magnetic susceptibility of the particles were characterized by XRD, TEM, CPS, DLS, BET and VSM measurements respectively. Further on, the introduction of crystalline defects into ZnO nanostructures can also assist in light activation for improved dye degradation. Band gap of a material and its absorbance is a concrete indicator for photocatalytic activity of the material. Due to high surface area, high porosity and affinity towards metal ions and availability of active surface sites, iron oxide nanoparticles show promising application in adsorption of heavy metal ions. An additional advantage of having magnetic based nanocomposite is, it offers magnetic field responsive separation and recovery of the catalyst. Therefore, we believe that ZnO linked Fe3O4 nanosystem would be efficient and reusable. Improved photocatalytic efficiency in addition to adsorption for environmental remediation has been a long standing challenge, and the nano-composite system offers the best of features which the two individual metal oxides provide for nanoremediation.

Keywords: adsorption, nanocomposite, nanoremediation, photocatalysis

Procedia PDF Downloads 237

Authors: Irfan Turetgen

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Closed-circuit cooling towers are cooling units that operate according to the indirect cooling principle. Unlike the open-loop cooling tower, the filler material includes a closed-loop water-operated heat exchanger. The main purpose of this heat exchanger is to prevent the cooled process water from contacting with the external environment. In order to ensure that the hot water is cooled, the water is cooled by the air flow and the circulation water of the tower as it passes through the pipe. They are now more commonly used than open loop cooling towers that provide cooling with plastic filling material. As with all surfaces in contact with water, there is a biofilm formation on the outer surface of the pipe. Although biofilm has been studied very well on plastic surfaces in open loop cooling towers, studies on biofilm layer formed on the heat exchangers of the closed circuit tower have not been found. In the recent study, natural biofilm formation was observed on the heat exchangers of the closed loop tower for 6 months. At the same time, nano-silica coating, which is known to reduce the formation of the biofilm layer, a comparison was made between the two different surfaces in terms of biofilm formation potential. Test surfaces were placed into biofilm reactor along with the untreated control coupons up to 6-months period for biofilm maturation. Natural bacterial communities were monitored to analyze the impact to mimic the real-life conditions. Surfaces were monthly analyzed in situ for their microbial load using epifluorescence microscopy. Wettability is known to play a key role in biofilm formation on surfaces, because characteristics of surface properties affect the bacterial adhesion. Results showed that surface-conditioning with nano-silica significantly reduce (up to 90%) biofilm formation. Easy coating process is a facile and low-cost method to prepare hydrophobic surface without any kinds of expensive compounds or methods.

Keywords: biofilms, cooling towers, fill material, nano silica

Procedia PDF Downloads 129

Authors: Sunil P. Lonkar, Vishnu V. Pillai, Saeed Alhassan

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Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

Procedia PDF Downloads 136

Authors: H. Saikouk, D. Laux, Emmanuel Le Clézio, B. Lacroix, K. Audic, R. Largenton, E. Federici, G. Despaux

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Pressurized Water Reactor (PWR) fuel rods are made of ceramic pellets (e.g. UO2 or (U,Pu) O2) assembled in a zirconium cladding tube. By design, an initial gap exists between these two elements. During irradiation, they both undergo transformations leading progressively to the closure of this gap. A local and non destructive examination of the pellet/cladding interface could constitute a useful help to identify the zones where the two materials are in contact, particularly at high burnups when a strong chemical bonding occurs under nominal operating conditions in PWR fuel rods. The evolution of the pellet/cladding bonding during irradiation is also an area of interest. In this context, the Institute of Electronic and Systems (IES- UMR CNRS 5214), in collaboration with the Alternative Energies and Atomic Energy Commission (CEA), is developing a high frequency acoustic microscope adapted to the control and imaging of the pellet/cladding interface with high resolution. Because the geometrical, chemical and mechanical nature of the contact interface is neither axially nor radially homogeneous, 2D images of this interface need to be acquired via this ultrasonic system with a highly performing processing signal and by means of controlled displacement of the sample rod along both its axis and its circumference. Modeling the multi-layer system (water, cladding, fuel etc.) is necessary in this present study and aims to take into account all the parameters that have an influence on the resolution of the acquired images. The first prototype of this microscope and the first results of the visualization of the inner face of the cladding will be presented in a poster in order to highlight the potentials of the system, whose final objective is to be introduced in the existing bench MEGAFOX dedicated to the non-destructive examination of irradiated fuel rods at LECA-STAR facility in CEA-Cadarache.

Keywords: high-frequency acoustic microscopy, multi-layer model, non-destructive testing, nuclear fuel rod, pellet/cladding interface, signal processing

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Authors: Anna Stepien

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The paper presents the results of research on modifications of sand-lime bricks, especially using glass additives (glass fiber and glass sand) and other additives (e.g.:basalt&barite aggregate, lithium silicate and microsilica) as well. The main goal of this paper is to answer the question ‘How to use glass additives in the sand-lime mass and get a better bricks?’ The article contains information on modification of sand-lime bricks using glass fiber, glass sand, microsilica (different structure of silica). It also presents the results of the conducted compression tests, which were focused on compressive strength, water absorption, bulk density, and their microstructure. The Scanning Electron Microscope, spectrum EDS, X-ray diffractometry and DTA analysis helped to define the microstructural changes of modified products. The interpretation of the products structure revealed the existence of diversified phases i.e.the C-S-H and tobermorite. CaO-SiO2-H2O system is the object of intensive research due to its meaning in chemistry and technologies of mineral binding materials. Because the blocks are the autoclaving materials, the temperature of hydrothermal treatment of the products is around 200°C, the pressure - 1,6-1,8 MPa and the time - up to 8hours (it means: 1h heating + 6h autoclaving + 1h cooling). The microstructure of the products consists mostly of hydrated calcium silicates with a different level of structural arrangement. The X-ray diffraction indicated that the type of used sand is an important factor in the manufacturing of sand-lime elements. Quartz sand of a high hardness is also a substrate hardly reacting with other possible modifiers, which may cause deterioration of certain physical and mechanical properties. TG and DTA curves show the changes in the weight loss of the sand-lime bricks specimen against time as well as the endo- and exothermic reactions that took place. The endothermic effect with the maximum at T=573°C is related to isomorphic transformation of quartz. This effect is not accompanied by a change of the specimen weight. The next endothermic effect with the maximum at T=730-760°C is related to the decomposition of the calcium carbonates. The bulk density of the brick it is 1,73kg/dm3, the presence of xonotlite in the microstructure and significant weight loss during DTA and TG tests (around 0,6% after 70 minutes) have been noticed. Silicate elements were assessed on the basis of their compressive property. Orthogonal compositional plan type 3k (with k=2), i.e.full two-factor experiment was applied in order to carry out the experiments both, in the compression strength test and bulk density test. Some modification (e.g.products with barite and basalt aggregate) have improved the compressive strength around 41.3 MPa and water absorption due to capillary raising have been limited to 12%. The next modification was adding glass fiber to sand-lime mass, then glass sand. The results show that the compressive strength was higher than in the case of traditional bricks, while modified bricks were lighter.

Keywords: bricks, fiber, glass, microstructure

Procedia PDF Downloads 347

Authors: Xiangjun Li, Huaiyuan Tian, Wujie Zhang, Dianhua Liu

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Polyoxymethylene dimethyl ethers (PODE_n) as clean diesel additive can improve the combustion efficiency and quality of diesel fuel and alleviate the problem of atmospheric pollution. Considering synthetic routes, PODE production from methanol and formaldehyde is regarded as the most economical and promising synthetic route. However, methanol used for synthesizing PODE can produce water, which causes the loss of active center of catalyst and hydrolysis of PODE_n in the production process. Macroporous strong acidic cation exchange resin catalyst was prepared, which has comparative advantages over other common solid acid catalysts in terms of stability and catalytic efficiency for synthesizing PODE. Catalytic reactions were carried out under 353 K, 1 MPa and 3mL·g_cat^-1·h^-1 in a fixed bed reactor. Methanol conversion and PODE_3-6 selectivity reached 49.91% and 23.43%, respectively. Catalyst lifetime evaluation showed that resin catalyst retained its catalytic activity for 20 days without significant changes and catalytic activity of completely deactivated resin catalyst can basically return to previous level by simple acid regeneration. The acid exchange capacities of original and deactivated catalyst were 2.5191 and 0.0979 mmol·g^-1, respectively, while regenerated catalyst reached 2.0430 mmol·g^-1, indicating that the main reason for resin catalyst deactivation is that Brønsted acid sites of original resin catalyst were temporarily replaced by non-hydrogen ion cations. A separation process consisting of extraction and distillation for PODE_3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE_3-6, respectively. The concentration of PODE_3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE_3-6 from methanol and formaldehyde solution is feasible.

Keywords: inactivation, polyoxymethylene dimethyl ethers, separation process, sulfonic cation exchange resin

Procedia PDF Downloads 137

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

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

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Sadat Sembatya

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Tantalum metal is used in addressing capacitance challenge in the 21st-century technology growth. Tantalum is rarely found in its elemental form. Hence it’s often found with niobium and the radioactive elements of thorium and uranium. Industrial processes are required to extract pure tantalum. Its deposits are mainly oxide associated and exist in Ta-Nb oxides such as tapiolite, wodginite, ixiolite, rutile and pyrochlore-supergroup minerals are of minor importance. The stability and chemical inertness of tantalum makes it a valuable substance for laboratory equipment and a substitute for platinum. Each period of Tantalum ore formation is characterized by specific mineralogical and geochemical features. Compositions of Columbite-Group Minerals (CGM) are variable: Fe-rich types predominate in the Man Shield (Sierra Leone), the Congo Craton (DR Congo), the Kamativi Belt (Zimbabwe) and the Jos Plateau (Nigeria). Mn-rich columbite-tantalite is typical of the Alto Ligonha Province (Mozambique), the Arabian-Nubian Shield (Egypt, Ethiopia) and the Tantalite Valley pegmatites (southern Namibia). There are large compositional variations through Fe-Mn fractionation, followed by Nb-Ta fractionation. These are typical for pegmatites usually associated with very coarse quartz-feldspar-mica granites. They are young granitic systems of the Kibara Belt of Central Africa and the Older Granites of Nigeria. Unlike ‘simple’ Be-pegmatites, most Ta-Nb rich pegmatites have the most complex zoning. Hence we need systematic exploration tools to find and rapidly assess the potential of different pegmatites. The pegmatites exist as known deposits (e.g., abandoned mines) and the exposed or buried pegmatites. We investigate rocks and minerals to trace for the possibility of the effect of hydrothermal alteration mainly for exposed pegmatites, do mineralogical study to prove evidence of gradual replacement and geochemistry to report the availability of trace elements which are good indicators of mineralisation. Pegmatites are not good geophysical responders resulting to the exclusion of the geophysics option. As for more advanced prospecting, we bulk samples from different zones first to establish their grades and characteristics, then make a pilot test plant because of big samples to aid in the quantitative characterization of zones, and then drill to reveal distribution and extent of different zones but not necessarily grade due to nugget effect. Rapid assessment tools are needed to assess grade and degree of fractionation in order to ‘rule in’ or ‘rule out’ a given pegmatite for future work. Pegmatite exploration is also unique, high risk and expensive hence right traceability system and certification for 3Ts are highly needed.

Keywords: exploration, mineralogy, pegmatites, tantalum

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Authors: Kanik Sharma

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In the year of 2011, the global production of carbon nano-materials (CNMs) was around 3,500 tons, and it is projected to expand at a compound annual growth rate of 30.6%. Expanding markets for applications of CNMs, such as carbon nano-tubes (CNTs) and carbon nano-fibers (CNFs), place ever-increasing demands on lowering their production costs. Current technologies for CNM generation require intensive premium feedstock consumption and employ costly catalysts; they also require input of external energy. Industrial-scale CNM production is conventionally achieved through chemical vapor deposition (CVD) methods which consume a variety of expensive premium chemical feedstocks such as ethylene, carbon monoxide (CO) and hydrogen (H2); or by flame synthesis techniques, which also consume premium feedstock fuels. Additionally, CVD methods are energy-intensive. Renewable and replenishable feedstocks, such as those found in municipal, industrial, agricultural recycling streams have a more judicious reason for usage, in the light of current emerging needs for sustainability. Agricultural sugarcane bagasse and corn residues, scrap tire chips as well as post-consumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings when either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation result in the formation of gaseous carbon-bearing effluents which when channeled into a heated reactor, produce CNMs, including carbon nano-tubes, catalytically synthesized therein on stainless steel meshes. The structure of the nano-material synthesized depends on the type of feedstock available for pyrolysis, and can be determined by analysing the feedstock. These feedstocks could supersede the use of costly and often toxic or highly-flammable chemicals such as hydrocarbon gases, carbon monoxide and hydrogen, which are commonly used as feedstocks in current nano-manufacturing process for CNMs.

Keywords: nanomaterials, waste plastics, sugarcane bagasse, pyrolysis

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Authors: J. B. J. Njalam’mano, E. M. N. Chirwa

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In low resource settings in Africa and other developing regions, pit latrines remain the dominant basic minimum acceptable form of sanitation. However, unpleasant smells-malodours emitted from faecal sludge in the pit latrines, which elicit disgusting or repulsive response, are one of the factors that thwart people to use latrines and instead opt for open defecation as an alternative. This provides an important but often overlooked major impediment, dissuading people from adopting and using the pit latrines hence affecting successful, effective sanitation promotion. The malodours are primarily attributed to four odorants: butanoic acid (C₄H₈O₂), dimethyl trisulphide (C₂H₆S₃), indole (C₈H₇N) and para-cresol (C₇H₈O). Several pit latrine deodorisation methods such as addition of carbonous materials, use of ventilation systems and urine separation are available, and they continue to occupy their niche, but social, economic, environmental and technological shortfalls remain. Bioremediation has been gaining popularity because it is inexpensive, simple to operate and environmentally friendly. Recently, the biodegradation of butanoic acid as individual odorant has been studied. However, to the best of our knowledge, there have been no kinetic studies of the butanoic acid in the presence of other key odorous compounds. In this study, a series of experiments were conducted to investigate the effects of indole on the removal of butanoic acid under aerobic conditions using indigenous bacteria strains, Pseudomonas aeruginosa, and Serratia marcescens isolated from faecal sludge as pure cultures as well as mixed cultures. In this purpose, butanoic acid removal was performed in a batch reactor containing the bacterial strains in mineral salt medium (MSM) amended with 3000 ppm of butanoic acid at the temperature of 30°C, under continuous stirring rate of 150 rpm and the concentration of indole was varied from 50-200 ppm. The initial pH of the solution was in the range of 6.0-7.2. Overall, there were significant differences in the bacterial growth rate and total butanoic acid removal dependent on the concentration of indole in the solution.

Keywords: biodegradation, butanoic acid, indole, pit latrine

Procedia PDF Downloads 195