Search results for: chemical looping partial oxidation of methane

Authors: A.Velavan, C. G. Saravanan, M. Vikneswaran, E. James Gunasekaran

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In present investigation, experiments were carried out to compare the effect of the ceramic coated piston crown and uncoated piston on combustion, performance and emission characteristics of a port injected Spark Ignited engine. The piston crown was coated with aluminium alloy in the form ceramic oxide layer of thickness 500 µm using micro-arc oxidation technique. This ceramic coating will act as a thermal barrier which reduces in-cylinder heat rejection and increases the durability of the piston by withstanding high temperature and pressure produced during combustion. Flame visualization inside the combustion chamber was carried out using AVL Visioscope combustion analyzer to predict the type of combustion occurs at different load condition. Based on the experimental results, it was found that the coated piston shows an improved thermal efficiency when compared to uncoated piston. This is because more heat presents in the combustion chamber which helps efficient combustion of the fuel. The CO and HC emissions were found to be reduced due to better combustion of the fuel whereas NOx emission was increased due to increase in combustion temperature for ceramic coated piston.

Keywords: coated piston, micro-arc oxidation, thermal barrier, thermal efficiency, visioscope

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Authors: T. H. N. Nguyen, A. Khodan, M. Amamra, J-V. Vignes, A. Kanaev

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The ultraporous nanofibrous alumina (NOA, Al2O3·nH2O) was synthesized by oxidation of laminated aluminium plates through a liquid mercury-silver layer in a humid atmosphere ~80% at 25°C. The material has an extremely high purity (99%), porosity (90%) and specific area (300 m2/g). The subsequent annealing of raw NOA permits obtaining pure transition phase (γ and θ) nanostructured materials. In this combination, we report on chemical, structural and phase transformations of pure and modified NOA by an impregnation of trimethylethoxysilane (TMES) and tetraethoxysilane (TEOS) during thermal annealing in the temperature range between 20 and 1650°C. The mass density, specific area, average diameter and specific area are analysed. The 3D model of pure NOA monoliths and silica modified NOA is proposed, which successfully describes the evolution of specific area, mass density and phase transformations. Activation energies of the mass transport in two regimes of surface diffusion and bulk sintering were obtained based on this model. We conclude about a common origin of modifications of the NOA morphology, chemical composition and phase transition.

Keywords: nanostructured materials, alumina (Al₂O₃), morphology, phase transitions

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Authors: Sutar Rani Ananda, M. V. Murugendrappa

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To investigate electrical properties of conducting polypyrrole (PPy) and cobalt aluminum oxide (CAO) nanocomposites, impedance analyzer in frequency range of 100 Hz to 5 MHz is used. In this work, PPy/CAO nanocomposites were synthesized by chemical oxidation polymerization method in different weight percent of CAO in PPy. The dielectric properties and AC conductivity studies were carried out for different nanocomposites in temperature range of room temperature to 180 °C. With the increase in frequency, the dielectric constant for all the nanocomposites was observed to decrease. AC conductivity of PPy was improved by addition of CAO nanopowder.

Keywords: polypyrrole, dielectric constant, dielectric loss, AC conductivity

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Authors: Askar Sabet, Abdolrasoul Fakhraee, Motahahre Ramezanpour, Noorallah Alipour

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An efficient and green method for oxidation of thiols to the corresponding disulfides is reported using ionic liquid [HSO3N(C2H4OSO3H)3] in the presence of free nano-Fe2O3 at 60°C. Ionic liquid is selective oxidant for S-S Coupling variety aliphatic and aromatic of thiols to corresponding disulfide in the presence of free nano-Fe2O3 as recoverable catalyst. Reaction has been performed in methanol as an inexpensive solvent. This reaction is clean and easy work-up with no side reaction.

Keywords: thiol, disulfide, ionic liquid, free nano-Fe2O3, oxidation, coupling

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Authors: A. V. Shelke, P. S. More

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This research aimed to study the kinetic reaction of reused cooking oil and to find the optimum condition of its process. The feedstock was collected from the street sellers and also prepared at laboratory. From this research, it is found that the kinetic reaction of reused sunflower oil (auto-oxidation) is obtained in terms of variation of the absorption coefficient of unexposed sunflower oil as 0.05 which is very close to that of exposed sunflower oil 0.075. At room temperature, the optimum intensity obtained from optical absorption spectroscopy study is 0.267 for unexposed sunflower oil and 0.194 for exposed sunflower oil. However, results indicated that FTIR spectroscopy is accurate and precise enough for such determination. Free Fatty Acid (FFA% = 026), acid ~53% and safonication ~%192 get reduce in exposed oil was investigated.

Keywords: friction, oxidation, sunflower oil, vegetable oils

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Authors: O. Tovide, N. Jahed, N. Mohammed, C. E. Sunday, H. R. Makelane, R. F. Ajayi, K. M. Molapo, A. Tsegaye, M. Masikini, S. Mailu, A. Baleg, T. Waryo, P. G. Baker, E. I. Iwuoha

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A graphenated–polyaniline (GR-PANI) nanocomposite sensor was constructed and used for the determination of anthracene. The direct electro-oxidation behavior of anthracene on the GR-PANI modified glassy carbon electrode (GCE) was used as the sensing principle. The results indicate thatthe response profile of the oxidation of anthracene on GR-PANI-modified GCE provides for the construction of sensor systems based onamperometric and potentiometric signal transductions. A dynamic linear range of 0.12- 100 µM anthracene and a detection limit of 0.044 µM anthracene were established for the sensor system.

Keywords: electrochemical sensors, environmental pollutants, graphenated-polymers, polyaromatic hydrocarbon

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Authors: A. Brener, B. Ismailov, G. Berdalieva

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In the paper we submit the modification of kinetic Smoluchowski equation for binary aggregation applying to systems with chemical reactions of first and second orders in which the main product is insoluble. The goal of this work is to create theoretical foundation and engineering procedures for calculating the chemical apparatuses in the conditions of joint course of chemical reactions and processes of aggregation of insoluble dispersed phases which are formed in working zones of the reactor.

Keywords: binary aggregation, clusters, chemical reactions, insoluble phases

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Authors: M. Sneha Reddy, M. Arun Kumar, V. Kameswara Rao

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Chromites are binary transition metal oxides with a general formula of ACr₂O₄, where A = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, and Cu²⁺. Chromites have a normal-type spinel structure with interesting applications in the areas of applied physics, material sciences, and geophysics. They have attracted great consideration because of their unique physicochemical properties and tremendous technological applications in nanodevices, sensor elements, and high-temperature ceramics with useful optical properties. Copper chromite is one of the most efficient spinel oxides, having pronounced commercial application as a catalyst in various chemical reactions like oxidation, hydrogenation, alkylation, dehydrogenation, decomposition of organic compounds, and hydrogen production. Apart from its usage in chemical industries, CuCr₂O₄ finds its major application as a burn rate modifier in solid propellant processing for space launch vehicles globally. Herein we synthesized the nanoparticles of copper chromite using the co-precipitation method. The synthesized nanoparticles were characterized by XRD, TEM, SEM, BET, and TG-DTA. The synthesized nanoparticles of copper chromites were used as a catalyst for the thermal decomposition of various high-energy materials.

Keywords: copper chromite, coprecipitation method, high energy materials, catalytic thermal decomposition

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

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

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

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Authors: Zuoyong Zhang, Min Yu, Jinlong Zhao, Shudong He

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The Maillard reaction can produce the flavor enhancing substance through the chemical crosslinking between free amino group of the protein or polypeptide with the carbonyl of the reducing sugar. In this research, solutions of rapeseed meal peptide and D-xylose with or without L-cysteine (RXC or RX) were heated over a range of temperatures (80-140 °C) for 2 h. It was observed that RXs had a severe browning,while RXCs accompanied by more pH decrement with the temperature increasing. Then the correlation among data of quantitative sensory descriptive analysis, free amino acid (FAA) and GC–MS of RXCs and RXs were analyzed using the partial least square regression method. Results suggested that the Maillard reaction product (MRPs) with cysteine formed at 120 °C (RXC-120) had greater sensory properties especially meat-like flavor compared to other MRPs. Meanwhile, it revealed that glutamic and glycine not only had a positive contribution to meaty aroma but also showed a significant and positive influence on umami taste of RXs based on the FAA data. Moreover, the sulfur-containing compounds showed a significant positive correlation with the meat-like flavor of RXCs, while RXs depended on furans and nitrogenous-containing compounds with more caramel-like flavor. Therefore, a MRP with strong meaty flavor could be obtained at 120 °C by addition of cysteine.

Keywords: rapeseed meal, Maillard reaction, sensory characteristics, FAA, GC–MS, partial least square regression

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Authors: Adriana Sosa, Susana Rincon, Chérif Ben, Diana Cabañas, Juan E. Ruiz, Alejandro Zepeda

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The complex chemical composition (mixtures of ammonium and recalcitrant compounds) of the effluents from the chemical, pharmaceutical and petrochemical industries represents a challenge in their biological treatment. This treatment involves nitrification process that can suffer an inhibition due to the presence of aromatic compounds giving as a result the decrease of the process efficiency. The inhibitory effects on nitrification in the presence of aromatic compounds have already been studied; however a few studies have considered the presence of phenolic compounds in the form of mixtures, which is the form that they are present in real context. For this reason, we realized a kinetic study on the nitrifying process in the presence of different concentrations of a mixture of phenol, o-cresol, m-cresol and p-cresol (0 - 320 mg C/L) in a sequencing batch reactor (SBR). Firstly, the nitrifying process was evaluated in absence of the phenolic mixture (control 1) in a SBR with 2 L working volume and 176 mg/L of nitrogen of microbial protein. Total oxidation of initial ammonium (efficiency; ENH4+ of 100 %) to nitrate (nitrifying yield; YNO3- of 0.95) were obtained with specific rates of ammonium consumption (qN-NH4+) and nitrate production (qN-NO3-) (of 1.11 ± 0.04 h-1 and 0.67 h-1 ± 0.11 respectively. During the phase of acclimation with 40 mg C/L of the phenolic mixture, an inhibitory effect on the nitrifying process was observed, provoking a decrease in ENH4+ and YNO3- (11 and 54 % respectively) as well as in the specific rates (89 y 46 % respectively), being the ammonia oxidizing bacteria (BAO) the most affected. However, in the next cycles without the phenolic mixture (control 2), the nitrifying consortium was able to recover its nitrifying capacity (ENH4+ = 100% and YNO3-=0.98). Afterwards the SBR was fed with 10 mg C/L of the phenolic mixture, obtaining and ENH4+ of 100%, YNO3- and qN-NH4+ 0.62 ± 0.006 and 0.13 ± 0.004 respectively, while the qN-NO3- was 0.49 ± 0.007. Moreover, with the increase of the phenolic concentrations (10-160 mg C/L) and the number of cycles the nitrifying consortium was able to oxidize the ammonia with ENH4+ of 100 % and YNO3- close to 1. However a decrease in the values of the nitrification specific rates and increase in the oxidation in phenolic compounds (70 to 94%) were observed. Finally, in the presence of 320 mg C/L, the nitrifying consortium was able to simultaneously oxidize the ammonia (ENH4+= 100%) and the phenolic mixture (p-cresol>phenol>m-cresol>o-cresol) being the o-cresol the most recalcitrant compound. In all the experiments the use of a SBR allowed a respiratory adaptation of the consortium to oxidize the phenolic mixture achieving greater adaptation of the nitrite-oxidizing bacteria (NOB) than in the ammonia-oxidizing bacteria (AOB).

Keywords: cresol, inhibition, nitrification, phenol, sequencing batch reactor

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Authors: Malika Foudia, Larbi Zerroual

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The objective of this work is to improve the electrical proprieties of lead-acid battery with the addition of additives in electrolyte and in the cured plates before oxidation. The results showed that the addition of surfactant in sulfuric acid and 3% mineral additive in the cured plates change the morphology and the crystallite size of PAM after oxidation. The discharge capacity increases with the decrease of the crystallite size and the resistance of the active mass. This shows that the addition of mineral additive and the surfactant additive to the PAM, the electrical performance and the cycle life of lead- acid battery are significantly increases.

Keywords: lead-acid battery, additives, positive plate, impedance (EIS).

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Authors: Rocio López, Miriam Tena, Montserrat Pérez, Rosario Solera

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Biotransformation of organic waste into biogas is considered an interesting alternative for the production of clean energy from renewable sources by reducing the volume and organic content of waste Anaerobic digestion is considered one of the most efficient technologies to transform waste into fertilizer and biogas in order to obtain electrical energy or biofuel within the concept of the circular economy. Currently, three types of anaerobic processes have been developed on a commercial scale: (1) single-stage process where sludge bioconversion is completed in a single chamber, (2) two-stage process where the acidogenic and methanogenic stages are separated into two chambers and, finally, (3) temperature-phase sequencing (TPAD) process that combines a thermophilic pretreatment unit prior to mesophilic anaerobic digestion. Two-stage processes can provide hydrogen and methane with easier control of the first and second stage conditions producing higher total energy recovery and substrate degradation than single-stage processes. On the other hand, co-digestion is the simultaneous anaerobic digestion of a mixture of two or more substrates. The technology is similar to anaerobic digestion but is a more attractive option as it produces increased methane yields due to the positive synergism of the mixtures in the digestion medium thus increasing the economic viability of biogas plants. The present study focuses on the energy recovery by anaerobic co-digestion of sewage sludge and waste from the aquaculture-fishing sector. The valorization is approached through the application of a temperature sequential phase process or TPAD technology (Temperature - Phased Anaerobic Digestion). Moreover, two-phase of microorganisms is considered. Thus, the selected process allows the development of a thermophilic acidogenic phase followed by a mesophilic methanogenic phase to obtain hydrogen (H₂) in the first stage and methane (CH₄) in the second stage. The combination of these technologies makes it possible to unify all the advantages of these anaerobic digestion processes individually. To achieve these objectives, a sequential study has been carried out in which the biochemical potential of hydrogen (BHP) is tested followed by a BMP test, which will allow checking the feasibility of the two-stage process. The best results obtained were high total and soluble COD yields (59.8% and 82.67%, respectively) as well as H₂ production rates of 12LH₂/kg SVadded and methane of 28.76 L CH₄/kg SVadded for TPAD.

Keywords: anaerobic co-digestion, TPAD, two-phase, BHP, BMP, sewage sludge, fish waste

Procedia PDF Downloads 138

Authors: H. Boukhatem, L. Djouadi, H. Khalaf, R. M. Navarro, F. V. Ganzalez

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Synthetic organic dyes are used in various industries, such as textile industry, leather tanning industry, paper production, hair dye production, etc. Wastewaters containing these dyes may be harmful to the environment and living organisms. Therefore, it is very important to remove or degrade these dyes before discharging them into the environment. In addition to standard technologies for the degradation and/or removal of dyes, several new specific technologies, the so-called advanced oxidation processes (AOPs), have been developed to eliminate dangerous compounds from polluted waters. AOPs are all characterized by the same chemical feature: production of radicals (•OH) through a multistep process, although different reaction systems are used. These radicals show little selectivity of attack and are able to oxidize various organic pollutants due to their high oxidative capacity (reduction potential of HO• Eo = 2.8 V). Heterogeneous photocatalysis, as one of the AOPs, could be effective in the oxidation/degradation of organic dyes. A major advantage of using heterogeneous photocatalysis for this purpose is the total mineralization of organic dyes, which results in CO2, H2O and corresponding mineral acids. In this study, nanomaterials based on montmorillonite and CuxCd1-xS with different Cu concentration (0.3 < x < 0.7) were utilized for the degradation of the commercial cationic textile dye Methylene blue (MB), used as a model pollutant. The synthesized nanomaterials were characterized by fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG–DTA). Test results of photocatalysis of methylene blue under UV-Visible irradiation show that the photoactivity of nanomaterials montmorillonite/ CuxCd1-xS increases with the increasing of Cu concentration. The kinetics of the degradation of the MB dye was described with the Langmuir–Hinshelwood (L–H) kinetic model.

Keywords: heterogeneous photocatalysis, methylene blue, montmorillonite, nanomaterial

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Authors: Angie Quevedo, Juan Bussi, Nestor Tancredi, Juan Fajardo-Díaz, Florentino López-Urías, Emilio Muñóz-Sandoval

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In this work, we study the carbon nanotubes (CNTs) formation by catalytic chemical vapor deposition (CCVD) over a catalyst with 20 % of Ni supported over La₂Zr₂O₇ (Ni20LZO). The high C solubility of Ni made it one of the most used in CNTs synthesis. Nevertheless, Ni presents also sintering and coalescence at high temperature. These troubles can be reduced by choosing a suitable support. We propose La₂Zr₂O₇ as for this matter since the incorporation of Ni by co-precipitation and calcination at 900 °C allows a good dispersion and interaction of the active metal (in the oxidized form, NiO) with this support. The CCVD was performed using 1 g of Ni20LZO at 950 °C during 30 min in Ar:H₂ atmosphere (2.5 L/min). The precursor, benzylamine, was added by a nebulizer-sprayer. X ray diffraction study shows the phase separation of NiO and La₂Zr₂O₇ after the calcination and the reduction to Ni after the synthesis. Raman spectra show D and G bands with a ID/IG ratio of 0.75. Elemental study verifies the incorporation of 1% of N. Thermogravimetric analysis shows the oxidation process start at around 450 °C. Future studies will determine the application potential of the samples.

Keywords: N doped carbon nanotubes, catalytic chemical vapor deposition, nickel catalyst, bimetallic oxide

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Authors: Luís R. Silva, Ana C. Gonçalves, Catarina Bento, Fábio Jesus, Branca M. Silva

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Prunus avium Linnaeus, more known as sweet cherry, is one of the most appreciated fruit worldwide. Most of these quantities are produced in Fundão region, being Saco the cultivar most produced. Saco is very rich in bioactive compounds, especially phenolics, and presents great antioxidant capacity. The purpose of the present study was to investigate the chemical profile and biological potential, concerning antioxidant, anti-diabetic activity and protective effects towards erythrocytes by Saco sweet cherry collected from Fundão region (Portugal). The hydroethanolic extracts were prepared and passed through a C18 solid-phase extraction column. The phenolic profile analyzed by LC-DAD method allowed to the identification of 22 phenolic compounds, being 16 non-phenolics and 6 anthocyanins. In respect to non-coloured phenolics, 3-O-caffeoylquinic and ρ-coumaroylquinic acids were the main ones. Concerning to anthocyanins, cyanidin-3-O-rutinoside was found in higher amounts. Relatively to biological potential, Saco showed great antioxidant potential, through DPPH and NO radical assays, with IC50 =16.24 ± 0.46 µg/mL and IC50 = 176.69 ± 3.35 µg/mL for DPPH and NO, respectively. These results were similar to those obtained for ascorbic acid control (IC50 = 16.92 ± 0.69 and IC50 = 162.66 ± 1.31 μg/mL for DPPH and NO, respectively). In respect to antidiabetic potential, Saco revealed capacity to inhibit α-glucosidase in a dose-dependent manner (IC50 = 10.79 ± 0.40 µg/mL), being much active than positive control acarbose (IC50 = 306.66 ± 0.84 μg/mL). Additionally, Saco extracts revealed protective effects against ROO•-mediated toxicity generated by AAPH in human blood erythrocytes, inhibiting hemoglobin oxidation (IC50 = 38.57 ± 0.96 μg/mL) and hemolysis (IC50 = 73.03 ± 1.48 μg/mL), in a concentration-dependent manner. However, Saco extracts were less effective than quercetin control (IC50 = 3.10 μg/mL and IC50 = 0.7 μg/mL for inhibition of hemoglobin oxidation and hemolysis, respectively). The results obtained showed that Saco is an excellent source of phenolic compounds. These ones are natural antioxidant substances, which easily capture reactive species. This work presents new insights regarding sweet cherry antioxidant properties which may be useful for the future development of new therapeutic strategies for preventing or attenuating oxidative-related disorders.

Keywords: antioxidant capacity, health benefits, phenolic compounds, saco

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Authors: Anastasios Rodis

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Background: Case studies of walkers, climbers, and campers exposed to cold and wet conditions without limb water/windproof protection revealed experiences of muscle weakness and fatigue. It is reasonable to assume that a part of the fatigue could occur due to an alteration in substrate utilization, since reduction of performance in extreme cold conditions, may partially be explained by higher anaerobic glycolysis, reflecting higher carbohydrate oxidation and an increase accumulation rate of blood lactate. The aim of this study was to assess the effects of pre-exercise lower limb cooling on substrate utilization rate during sub-maximal exercise. Method: Six male university students (mean (SD): age, 21.3 (1.0) yr; maximal oxygen uptake (V0₂ max), 49.6 (3.6) ml.min⁻¹; and percentage of body fat, 13.6 (2.5) % were examined in random order after either 30min cold water (12°C) immersion utilized as the cooling strategy up to the gluteal fold, or under control conditions (no precooling), with tests separated by minimum of 7 days. Exercise consisted of 60min cycling at 50% V0₂ max, in a thermoneutral environment of 20°C. Subjects were also required to record a diet diary over the 24hrs prior to the each trial. Means (SD) for the three macronutrients during the 1 day prior to each trial (expressed as a percentage of total energy) 52 (3) % carbohydrate, 31 (4) % fat, and 17 (± 2) % protein. Results: The following responses to lower limb cooling relative to control trial during exercise were: 1) Carbohydrate (CHO) oxidation, and blood lactate (Bₗₐc) concentration were significantly higher (P < 0.05); 2) rectal temperature (Tᵣₑc) was significantly higher (P < 0.05), but skin temperature was significantly lower (P < 0.05); no significant differences were found in blood glucose (Bg), heart rate (HR) and oxygen consumption (V0₂). Discussion: These data suggested that lower limb cooling prior to submaximal exercise will shift metabolic processes from Fat oxidation to CHO oxidation. This shift from Fat to CHO oxidation will probably have important implications in the surviving scenario, since people facing accidental localized cooling of their limbs either through wading/falling in cold water or snow even if they do not perform high intensity activity, they have to rely on CHO availability.

Keywords: exercise in wet conditions, leg cooling, outdoors exercise, substrate utilization

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Authors: F. Javier Benitez, Juan L. Acero, Francisco J. Real, Elena Rodriguez

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Five selected pollutants which are frequently present in waters and wastewaters have been degraded by the advanced oxidation process constituted by UV radiation activated with the additional presence of persulfate (UV/PS). These pollutants were 1H-benzotriazole (BZ), N,N-diethyl-m-toluamide or DEET (DT), chlorophene (CP), 3-methylindole (ML), and nortriptyline hydrochloride (NH).While UV radiation alone almost not degraded these substances, the addition of PS generated the very reactive and oxidizing sulfate radical SO₄⁻. The kinetic study provided the second order rate constants for the reaction between this radical and each pollutant. An increasing dose of PS led to an increase in the degradation rate, being the highest results obtained at near neutral pH. Several water matrices were tested, and the presence of bicarbonate showed different effects: a decrease in the elimination of DT, BZ, and NH; and an increase in the oxidation of CP and ML. The additional presence of humic acids (AH) decreased this degradation, because of several effects: light screening and radical scavenging. The presence of several natural substances in waters (both types, inorganic and organic matter) usually diminishes the oxidation rates of organic pollutants, but this combination UV/PS process seems to be an efficient solution for the removal of the selected contaminants when are present in contaminated waters.

Keywords: water purification, UV activated persulfate, kinetic study, sulfate radicals

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Authors: Y. S. Shen, B. H. Liao

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This study aimed to develop the design equation of a laminar-falling-film-slurry (LFFS) type photoreactor for the treatment of organic wastewaters containing isopropyl alcohol (IPA) by VUV-based advanced oxidation processes (AOPs). The photoreactor design equations were established by combining with the chemical kinetics of the photocatalytic system, light absorption model within the photoreactor, and was used to predict the decomposition of IPA in aqueous solutions in the photoreactors of different geometries at various operating conditions (volumetric flow rate, oxidants, catalysts, solution pH values, UV light intensities, and initial concentration of pollutants) to verify its rationality and feasibility. By the treatment of the LFFS-VUV only process, it was found that the decomposition rates of IPA in aqueous solutions increased with the increase of volumetric flow rate, VUV light intensity, dosages of TiO2 and H2O2. The removal efficiencies of IPA by photooxidation processes were in the order: VUV/H2O2>VUV/TiO2/H2O2>VUV/TiO2>VUV only. In VUV, VUV/H2O2, VUV/TiO2/H2O2 processes, integrating with the reaction kinetic equations of IPA, the mass conservation equation and the linear light source model, the photoreactor design equation can reasonably to predict reaction behaviors of IPA at various operating conditions and to describe the concentration distribution profiles of IPA within photoreactors.The results of this research can be useful basis for the future application of the homogeneous and heterogeneous VUV-based advanced oxidation processes.

Keywords: isopropyl alcohol, photoreactor design, VUV, AOPs

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Authors: Yaniv Knop, Alva Peled

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Over the past few years there has been a growing interest in the development of Portland Composite Cement, by partial replacement of the clinker with mineral additives. The motivations to reduce the clinker content are threefold: (1) Ecological - due to lower emission of CO2 to the atmosphere; (2) Economical - due to cost reduction; and (3) Scientific\Technology – improvement of performances. Among the mineral additives being used and investigated, limestone is one of the most attractive, as it is considered natural, available, and with low cost. The goal of the research is to develop green cement, by partial replacement of the clinker with limestone powder while improving the performances of the cement paste. This work studied blended cements with three limestone powder particle diameters: smaller than, larger than, and similarly sized to the clinker particle. Blended cement with limestone consisting of one particle size distribution and limestone consisting of a combination of several particle sizes were studied and compared in terms of hydration rate, hydration degree, and water demand to achieve normal consistency. The performances of these systems were also compared with that of the original cement (without added limestone). It was found that the ability to replace an active material with an inert additive, while achieving improved performances, can be obtained by increasing the packing density of the cement-based particles. This may be achieved by replacing the clinker with limestone powders having a combination of several different particle size distributions. Mathematical and physical models were developed to simulate the setting history from initial to final setting time and to predict the packing density of blended cement with limestone having different sizes and various contents. Besides the effect of limestone, as inert additive, on the packing density of the blended cement, the influence of the limestone particle size on three different chemical reactions were studied; hydration of the cement, carbonation of the calcium hydroxide and the reactivity of the limestone with the hydration reaction products. The main results and developments will be presented.

Keywords: packing density, hydration degree, limestone, blended cement

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Authors: Bothinah Altaf, Gary Montague, Elaine B. Martin

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This study involves the modeling and monitoring of an ammonia synthesis fixed-bed reactor using partial least squares (PLS) and its variants. The process exhibits complex dynamic behavior due to the presence of heat recycling and feed quench. One limitation of static PLS model in this situation is that it does not take account of the process dynamics and hence dynamic PLS was used. Although it showed, superior performance to static PLS in terms of prediction, the monitoring scheme was inappropriate hence adaptive PLS was considered. A limitation of adaptive PLS is that non-conforming observations also contribute to the model, therefore, a new adaptive approach was developed, robust adaptive dynamic PLS. This approach updates a dynamic PLS model and is robust to non-representative data. The developed methodology showed a clear improvement over existing approaches in terms of the modeling of the reactor and the detection of faults.

Keywords: ammonia synthesis fixed-bed reactor, dynamic partial least squares modeling, recursive partial least squares, robust modeling

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Authors: Mahmood Al Ramahi, G. Keszthelyi-Szabo, S. Beszedes

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Hydrothermal carbonization (HTC) is a thermochemical reaction that utilizes saturated water and vapor pressure to convert waste biomass to C-rich products This work evaluated the effect of HTC as a pre- and post-treatment technique to anaerobic digestion (AD) of dairy sludge, as information in this field is still in its infancy, with many research and methodological gaps. HTC effect was evaluated based on energy recovery, nutrients transformation, and sludge biodegradability. The first treatment approach was executed by applying hydrothermal carbonization (HTC) under a range of temperatures, prior to mesophilic anaerobic digestion (AD) of dairy sludge. Results suggested an optimal pretreatment temperature at 210 °C for 30 min. HTC pretreatment increased methane yield and chemical oxygen demand removal. The theoretical model based on Boyle’s equation had a very close match with the experimental results. On the other hand, applying HTC subsequent to AD increased total energy production, as additional energy yield was obtained by the solid fuel (hydrochar) beside the produced biogas. Furthermore, hydrothermal carbonization of AD digestate generated liquid products (HTC digestate) with improved chemical characteristics suggesting their use as liquid fertilizers.

Keywords: hydrothermal carbonization, anaerobic digestion, energy balance, sludge biodegradability, biogas

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Authors: Yves Mann Elate Lea Mbassi, Marie Solange Evehe Bebandoue, Wilfred Fon Mbacham

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Improving the catalytic performance of enzymes has been a long-standing theme of analytical biochemistry research. Induction of peroxidase activity by metals is a common reaction in higher plants. We thought that this increase in peroxidase activity may be due, on the one hand, to the stimulation of the gene expression of these enzymes but also to a modification of their chemical reactivity following the binding of some metal ions on their active site. We tested the effect of some metal salts (MgCl₂, MnCl₂, ZnCl₂, CaCl₂ and CuSO₄) on the activity and thermostability of peroxidase A6, a thermostable peroxidase that we discovered and purified in a previous study. The chromogenic substrate used was 3,3′,5,5′-tetramethylbenzidine. Of all the metals tested for their effect on A6, only magnesium and copper had a significant effect on the activity of the enzyme at room temperature. The Mann-Whitney test shows a slight inhibitory effect of activity by the magnesium salt (P = 0.043), while the activity of the enzyme is 5 times higher in the presence of the copper salt (P = 0.002). Moreover, the thermostability of peroxidase A6 is increased when calcium and copper salts are present. The activity in the presence of CaCl₂ is 8 times higher than the residual activity of the enzyme alone after incubation at 80°C for 10 min and 35 times higher in the presence of CuSO4 under the same conditions. In addition, manganese and zinc salts slightly reduce the thermostability of the enzyme. The activity and structural stability of peroxidase A6 can clearly be activated by Cu₂+, which therefore enhance the oxidation of 3,3′,5,5′-tetramethylbenzidine, which was used in this study as a chromogenic substrate. Ca₂+ likely has a more stabilizing function for the catalytic site.

Keywords: peroxidase activity, copper ions, calcium ions, thermostability

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Authors: Rui Tu, Yakui Bai, Huailin Li

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The lead-bismuth eutectic (LBE) alloy is a promising candidate of coolant in the fast neutron reactors and accelerator-driven systems (ADS) because of its good properties, such as low melting point, high neutron yields and high thermal conductivity. Although the corrosion of the structure materials caused by the liquid metal (LM) coolant is a challenge to the safe operating of a lead-bismuth eutectic nuclear reactor. Thermodynamic theories, experiential formulas and experimental data can be used for explaining the maintenance of the protective oxide layers on stainless steels under satisfaction oxygen concentration, but the atomic scale insights of such anti-corrosion mechanisms are little known. In the present work, the first-principles calculations are carried out to study the effects of oxygen partial pressure on the formation energies of the liquid metal coolant relevant impurity defects in the anti-corrosion oxide films on the surfaces of the structure materials. These approaches reveal the microscope mechanisms of the corrosion of the structure materials, especially for the influences from the oxygen partial pressure. The results are helpful for identifying a crucial oxygen concentration for corrosion control, which can ensure the systems to be operated safely under certain temperatures.

Keywords: oxygen partial pressure, liquid metal coolant, TDDFT, anti-corrosion layer, formation energy

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Authors: Ana Paula Mousinho, Ronaldo D. Mansano, Nelson Ordonez

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Carbon nanotubes are one of the main elements in nanotechnologies; their applications are in microelectronics, nano-electronics devices (photonics, spintronic), chemical sensors, structural material and currently in clean energy devices (supercapacitors and fuel cells). The use of magnetic particle decorated carbon nanotubes increases the applications in magnetic devices, magnetic memory, and magnetic oriented drug delivery. In this work, single-walled carbon nanotubes (CNTs) forest decorated with chromium were deposited at room temperature by high-density plasma chemical vapor deposition (HDPCVD) system. The CNTs forest was obtained using pure methane plasmas and chromium, as precursor material (seed) and for decorating the CNTs. Magnetron sputtering deposited the chromium on silicon wafers before the CNTs' growth. Scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy, and X-ray diffraction characterized the single-walled CNTs forest decorated with chromium. In general, the CNTs' spectra show a unique emission band, but due to the presence of the chromium, the spectra obtained in this work showed many bands that are related to the CNTs with different diameters. The CNTs obtained by the HDPCVD system are highly aligned and showed metallic features, and they can be used as photonic material, due to the unique structural and electrical properties. The results of this work proved the possibility of obtaining the controlled deposition of aligned single-walled CNTs forest films decorated with chromium by high-density plasma chemical vapor deposition system.

Keywords: CNTs forest, high density plasma deposition, high-aligned CNTs, nanomaterials

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Authors: Jiang-Bei Qin, Rui-Xia Miao, Wei Ren

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In this study, high crystalline gallium oxide microstructures (wires, belts, and sheets) were synthesized by catalyst-free thermal oxidation. Structural studies such as X-ray diffraction, Raman and transmission electron microscope (TEM) investigations on the microstructures showed monoclinic phase of gallium oxide and single crystalline structure. The scanning electron microscopy (SEM) observations revealed that a huge super microsheet even grows up to 450 µm in length and 206 µm in width. Gallium oxide microstructures exhibit high crystallinity along (002) and (401), respectively. The PL spectrum of these microstructures excites a blue light band centered at 441 and 489nm. The growth mechanism of gallium oxide microstructures is discussed. These gallium oxide microstructures have great potential in functional devices.

Keywords: catalyst-free, gallium oxide, microstructures, thermal oxide

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Authors: Muhammad Ajmal

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- Thermal processing and subsequent storage of ultra-heat treated (UHT) milk leads to alteration in protein profile, Maillard reaction and lipid oxidation. Concentration of carbohydrates in normal and flavored version of UHT milk is considerably different. Transition in protein profile, Maillard reaction and lipid oxidation in UHT flavored milk was determined for 90 days at ambient conditions and analyzed at 0, 45 and 90 days of storage. Protein profile, hydroxymethyl furfural, furosine, Nε-carboxymethyl-l-lysine, fatty acid profile, free fatty acids, peroxide value and sensory characteristics were determined. After 90 days of storage, fat, protein, total solids contents and pH were significantly less than the initial values determined at 0 day. As compared to protein profile normal UHT milk, more pronounced changes were recorded in different fractions of protein in UHT milk at 45 and 90 days of storage. Tyrosine content of flavored UHT milk at 0, 45 and 90 days of storage were 3.5, 6.9 and 15.2 µg tyrosine/ml. After 45 days of storage, the decline in αs1-casein, αs2-casein, β-casein, κ-casein, β-lactoglobulin, α-lactalbumin, immunoglobulin and bovine serum albumin were 3.35%, 10.5%, 7.89%, 18.8%, 53.6%, 20.1%, 26.9 and 37.5%. After 90 days of storage, the decline in αs1-casein, αs2-casein, β-casein, κ-casein, β-lactoglobulin, α-lactalbumin, immunoglobulin and bovine serum albumin were 11.2%, 34.8%, 14.3%, 33.9%, 56.9%, 24.8%, 36.5% and 43.1%. Hydroxy methyl furfural content of UHT milk at 0, 45 and 90 days of storage were 1.56, 4.18 and 7.61 (µmol/L). Furosine content of flavored UHT milk at 0, 45 and 90 days of storage intervals were 278, 392 and 561 mg/100g protein. Nε-carboxymethyl-l-lysine content of UHT flavored milk at 0, 45 and 90 days of storage were 67, 135 and 343mg/kg protein. After 90 days of storage of flavored UHT milk, the loss of unsaturated fatty acids 45.7% from the initial values. At 0, 45 and 90 days of storage, free fatty acids of flavored UHT milk were 0.08%, 0.11% and 0.16% (p<0.05). Peroxide value of flavored UHT milk at 0, 45 and 90 days of storage was 0.22, 0.65 and 2.88 (MeqO²/kg). Sensory analysis of flavored UHT milk after 90 days indicated that appearance, flavor and mouth feel score significantly decreased from the initial values recorded at 0 day. Findings of this investigation evidenced that in flavored UHT milk more pronounced changes take place in protein profile, Maillard reaction products and lipid oxidation as compared to normal UHT milk.

Keywords: UHT flavored milk , hydroxymethyl furfural, lipid oxidation, sensory properties

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Authors: Thanida Sritangthong, Suksun Amornraksa

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By-product upgrading is crucial in hydrocarbon industries as it can increase overall profit margin of the business. Microwave-assisted pyrolysis is relatively new technique which induces heat directly to raw materials. This results in a more energy saving and more energy-efficient process. It is also a promising method to enhance and accelerate chemical reactions, thus reducing the pyrolysis reaction time and increasing the quality of value-added products from different kinds of feedstocks. In this study, upgrading opportunity of fuel oil by-product from an olefins plant is investigated by means of microwave pyrolysis. The experiment was conducted in a lab-scale quartz reactor placed inside a 1,100 watts household microwave oven. Operating temperature was varied from 500 to 900C to observe the consequence on the quality of pyrolysis products. Several microwave receptors i.e. activated carbon, silicon carbide (SiC) and copper oxide (CuO) were used as a material to enhance the heating and reaction in the reactor. The effect of residence time was determined by adjusting flow rate of N2 carrier gas. The chemical composition and product yield were analyzed by using gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). The results showed that hydrogen, methane, ethylene, and ethane were obtained as the main gaseous products from all operating temperatures while the main liquid products were alkane, cycloalkane and polycyclic aromatic groups. The results indicated that microwave pyrolysis has a potential to upgrade low value hydrocarbons to high value products.

Keywords: fuel oil, heavy hydrocarbons, microwave pyrolysis, pyrolysis

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Authors: Pankaj Kumar Das, Niranjan Kumar, Prasun Chakraborti

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Temperature dependent tribologiocal properties of nuclear grade turbostatic graphite were studied using 100Cr6 steel counterbody. High value of friction coefficient (0.25) and high wear loss was observed at room temperature and this value decreased to 0.1 at 150oC. Consequently, wear loss is also decreased. Such behavior is explained by oxidation/vaporization of graphite and water molecules. At room temperature, the adsorbed water in graphite does not decompose and effect of passivation mechanism does not work. However, at 150oC, the water decomposed into OH, atomic hydrogen and oxygen which efficiently passivates the carbon dangling bonds. This effect is known to decrease the energy of the contact and protect against abrasive wear.

Keywords: high temperature tribology, oxidation, turbostratic graphite, wear

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Authors: Youssef Abdelli, Rachid Nasri

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The large amplitude free vibration analysis of three-layered symmetric sandwich beams is carried out using two different approaches. The governing nonlinear partial differential equations of motion in free natural vibration are derived using Hamilton's principle. The formulation leads to two nonlinear partial differential equations that are coupled both in axial and binding deformations. In the first approach, the method of multiple scales is applied directly to the governing equation that is a nonlinear partial differential equation. In the second approach, we discretize the governing equation by using Galerkin's procedure and then apply the shooting method to the obtained ordinary differential equations. In order to check the validity of the solutions obtained by the two approaches, they are compared with the solutions obtained by two approaches; they are compared with the solutions obtained numerically by the finite difference method.

Keywords: finite difference method, large amplitude vibration, multiple scales, nonlinear vibration

Procedia PDF Downloads 444