Search results for: methanol oxidation reaction

Authors: Sonya Barzgar, J. Patrick, A. Hettiaratchi

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Methane (CH4) is reputed as the second largest contributor to greenhouse effect with a global warming potential (GWP) of 34 related to carbon dioxide (CO2) over the 100-year horizon, so there is a growing interest in reducing the emissions of this gas. Methane biofiltration (MBF) is a cost effective technology for reducing low volume point source emissions of methane. In this technique, microbial oxidation of methane is carried out by methane-oxidizing bacteria (methanotrophs) which use methane as carbon and energy source. MBF uses a granular medium, such as soil or compost, to support the growth of methanotrophic bacteria responsible for converting methane to carbon dioxide (CO₂) and water (H₂O). Even though the biofiltration technique has been shown to be an efficient, practical and viable technology, the design and operational parameters, as well as the relevant microbial processes have not been investigated in depth. In particular, limited research has been done on the effects of sulphur on methane bio-oxidation. Since bacteria require a variety of nutrients for growth, to improve the performance of methane biofiltration, it is important to establish the input quantities of nutrients to be provided to the biofilter to ensure that nutrients are available to sustain the process. The study described in this paper was conducted with the aim of determining the influence of sulphur on methane elimination in a biofilter. In this study, a set of experimental measurements has been carried out to explore how the conversion of elemental sulphur could affect methane oxidation in terms of methanotrophs growth and system pH. Batch experiments with different concentrations of sulphur were performed while keeping the other parameters i.e. moisture content, methane concentration, oxygen level and also compost at their optimum level. The study revealed the tolerable limit of sulphur without any interference to the methane oxidation as well as the particular sulphur concentration leading to the greatest methane elimination capacity. Due to the sulphur oxidation, pH varies in a transient way which affects the microbial growth behavior. All methanotrophs are incapable of growth at pH values below 5.0 and thus apparently are unable to oxidize methane. Herein, the certain pH for the optimal growth of methanotrophic bacteria is obtained. Finally, monitoring methane concentration over time in the presence of sulphur is also presented for laboratory scale biofilters.

Keywords: global warming, methane biofiltration (MBF), methane oxidation, methanotrophs, pH, sulphur

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

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

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

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Authors: Feny Mentang, Roike Iwan Montolalu, Henny Adeleida Dien, Kristhina P. Rahael, Tomy Moga, Ayub Meko, Siegfried Berhimpon

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Smoked fish is one of the famous fish products in North Sulawesi, Indonesia. Research in producing smoked fish using smoke liquid, and the use of that product as main taste for a new “natural condiment” have been done, including a series of researches to find materials for sachet. Research aims are to determine the effectiveness of smoked edible sachets, in preventing oxidation of natural condiment, stored in ambient temperature. Two kinds of natural condiment flavors were used, i.e. smoked Skipjack flavor, and Sea Food flavor. Three variables of edible sachets were used for the natural condiments, i.e. non-sachet, edible sachet without smoke liquid, and edible sachet with smoke liquid. The natural condiments were then stored in ambient temperature, for 0, 10, 20, and 30 days. To determine the effectiveness of edible sachets in preventing oxidation, analysis of TBA, water content, and pH were conducted. The results shown that natural condiment with smoked seafood taste had TBA values higher than that of smoked Skipjack. Edible sachet gave a highly significant effect (P > 0.01) on TBA. Natural condiment in smoked edible sachet has a lower TBA than natural condiment non-sachet, and with sachet without smoke liquid. The longer storing time, the higher TBA, especially for non-sachet and with sachet without smoke liquid. There were no significant effect (P > 0.05) of edible sachet on water content and pH.

Keywords: edible sachet, smoke liquid, natural condiment, oxidation

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Authors: Wanthani Paengsri, Thanyarat Chuesaard, Napapha Promsawan

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Spilanthes acmella Murr. was extracted with methanol, yielding methanol crude extract 5.86 %w/w. This study aimed to examine the chemical composition and antioxidant activity of methanolic crude extract. The chemical composition of methanolic crude extract was analyzed by gas chromatography-mass spectrometry (GC-MS). The predominant components were found to be palmitic acid (40.08%), 2-hexadecanoyl glycerol (6.96%) and octadecanoic acid (4.06%). Antioxidant activity was determined using 2,2-diphenyl-1-picryl hydrazyl (DPPH) free radical, for evaluating free radicle scavenging activity. The methanolic extract at 150 µg/mL showed an antioxidant activity with high of radical scavenging activity (75.23%).

Keywords: antioxidant activity, GC-MS analysis, Spilanthes, Phak-Kratt Hauwaen

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Authors: Mohammad Anwar, Shah Waliullah

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The development of science and technology in the present era has an urgent demand for the training of thinking of undergraduates. This requirement actively promotes research and teaching of basic theories, beneficial to the career development of students. This study clarified the dialectical relation between the thermodynamic equilibrium constant and reaction rate constant through the contrast thinking method. Findings reveal that both the isobaric Van't Hoff equation and the Arrhenius equation had four similar forms, and the change in the trend of both constants showed a similar law. By the derivation of the formation rate constant of the product (KY) and the consumption rate constant of the reactant (KA), the ratio of both constants at the end state indicated the nature of the equilibrium state in agreement with that of the thermodynamic equilibrium constant (K^θ (T)). This study has thus presented that the thermodynamic equilibrium constant contained the characteristics of microscopic dynamics based on the analysis of the reaction mechanism, and both constants are organically connected and unified. The reaction enthalpy and activation energy are closely related to each other with the same connotation.

Keywords: thermodynamic equilibrium constant, reaction rate constant, PBL teaching, dialectical relation, innovative thinking

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Authors: Saeed Ghali, Azza Ahmed, Taha Mattar

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Solid Oxide Fuel Cell (SOFC) is a promising solution for the energy resources leakage. Ferritic stainless steel becomes a suitable candidate for the SOFCs interconnects due to the recent advancements. Different steel alloys were designed to satisfy the needed characteristics in SOFCs interconnect as conductivity, thermal expansion and corrosion resistance. Refractory elements were used as alloying elements to satisfy the needed properties. The oxidation behaviour of the developed alloys was studied where the samples were heated for long time period at the maximum operating temperature to simulate the real working conditions. The formed scale and oxidized surface were investigated by SEM. Microstructure examination was carried out for some selected steel grades. The effect of alloying elements on the behaviour of the proposed interconnects material and the performance during the working conditions of the cells are explored and discussed. Refractory metals alloying of chromium steel seems to satisfy the needed characteristics in metallic interconnects.

Keywords: SOFCs, Cr-steel, interconnects, oxidation

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Authors: M. Abdoul-Hakim, A. Zeroual, H. Garmes

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2-Chlorobenzimidazoles are amphoteric compounds and versatile intermediates for the construction of polycyclic heterocycles. In this theoretical study performed by DFT at the B3LYP/6-311+G(d,p) level, we showed that the most likely route to obtain benzimidazo[1,2-d]oxadiazole from the reaction of 2-Chlorobenzimidazole with benzonitrile N-oxide involves the presence of anionic species, a concerted mechanism is not possible. The inclusion of the effect of the polar protic solvent (MeOH) favors the course of the reaction. The key interactions causing bond formation and breakage were identified by ELF topological analysis.

Keywords: benzimidazo[1, 2-d]oxadiazole, benzonitrile N-oxide, DFT, ELF, polycyclic heterocycles

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Authors: Michalina Aniola, Andrzej Katrusiak

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4,4-Bipyridine is an important compound often used in chemical practice and more recently frequently applied for designing new metal organic framework (MoFs). Here we present a systematic high-pressure study of its hydrobromide salt. 4,4-Bipyridine hydrobromide monohydrate, 44biPyHBrH₂O, at ambient-pressure is orthorhombic, space group P212121 (phase a). Its hydrostatic compression shows that it is stable to 1.32 GPa at least. However, the recrystallization above 0.55 GPa reveals a new hidden b-phase (monoclinic, P21/c). Moreover, when the 44biPyHBrH2O is heated to high temperature the chemical reactions of this compound in methanol solution can be observed. High-pressure experiments were performed using a Merrill-Bassett diamond-anvil cell (DAC), modified by mounting the anvils directly on the steel supports, and X-ray diffraction measurements were carried out on a KUMA and Excalibur diffractometer equipped with an EOS CCD detector. At elevated pressure, the crystal of 44biPyHBrH₂O exhibits several striking and unexpected features. No signs of instability of phase a were detected to 1.32 GPa, while phase b becomes stable at above 0.55 GPa, as evidenced by its recrystallizations. Phases a and b of 44biPyHBrH2O are partly isostructural: their unit-cell dimensions and the arrangement of ions and water molecules are similar. In phase b the HOH-Br- chains double the frequency of their zigzag motifs, compared to phase a, and the 44biPyH+ cations change their conformation. Like in all monosalts of 44biPy determined so far, in phase a the pyridine rings are twisted by about 30 degrees about bond C4-C4 and in phase b they assume energy-unfavorable planar conformation. Another unusual feature of 44biPyHBrH2O is that all unit-cell parameters become longer on the transition from phase a to phase b. Thus the volume drop on the transition to high-pressure phase b totally depends on the shear strain of the lattice. Higher temperature triggers chemical reactions of 44biPyHBrH2O with methanol. When the saturated methanol solution compound precipitated at 0.1 GPa and temperature of 423 K was required to dissolve all the sample, the subsequent slow recrystallization at isochoric conditions resulted in disalt 4,4-bipyridinium dibromide. For the 44biPyHBrH2O sample sealed in the DAC at 0.35 GPa, then dissolved at isochoric conditions at 473 K and recrystallized by slow controlled cooling, a reaction of N,N-dimethylation took place. It is characteristic that in both high-pressure reactions of 44biPyHBrH₂O the unsolvated disalt products were formed and that free base 44biPy and H₂O remained in the solution. The observed reactions indicate that high pressure destabilized ambient-pressure salts and favors new products. Further studies on pressure-induced reactions are carried out in order to better understand the structural preferences induced by pressure.

Keywords: conformation, high-pressure, negative area compressibility, polymorphism

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Authors: Anushree, Chhaya Sharma, Satish Kumar

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Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO₂ nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO₂ nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce₄₀Ni₆₀ catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: catalysis, nano-materials, NiO-CeO2, paper mill, wastewater, wet air oxidation

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Authors: Peikun Zhang, Chunhua Cui

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Photoelectrochemical (PEC) water splitting provides a promising pathway to convert solar energy into renewable fuels. However, the main and seemingly insurmountable obstacle is that the sluggish kinetics of oxygen evolution reaction (OER) severely jeopardizes the overall efficiency, thus exploring highly active, stable, and appreciable catalysts is urgently requested. Herein a competitive coordination strategy was demonstrated to form a reversible hybrid homo-heterogeneous catalyst for efficient OER in alkaline media. The dynamic process involves an in-situ anchoring of soluble nickel–bipyridine pre-catalyst to a conductive substrate under OER and a re-dissolution course under open circuit potential, induced by the competitive coordination between nickel–bipyridine and nickel-hydroxyls. This catalyst allows to elaborately self-modulate a charge-transfer layer thickness upon the catalytic on-off operation, which affords substantially increased active sites, yet remains light transparency, and sustains the stability of over 200 hours of continuous operation. The integration of this catalyst with exemplified state-of-the-art Ni-sputtered Si photoanode can facilitate a ~250 mV cathodic shift at a current density of 20 mA cm-2. This finding helps the understanding of catalyst from a “dynamic” perspective, which represents a viable alternative to address remaining hurdles toward solar-driven water oxidation.

Keywords: molecular catalyst, oxygen evolution reaction, solar energy, transition metal complex, water splitting

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Authors: Sajid Maqsood, Aysha Al Rashedi, Aisha Abushelaibi, Kusaimah Manheem

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Impact of different natural antioxidants on lipid oxidation, microbial load and sensorial quality in ground camel meat (leg region) during 9 days of refrigerated storage were investigated. Control camel meat showed higher lipid oxidation products (Peroxide value and Thiobarbituric acid reactive substances (TBARS)) during the storage period. Upon addition of different natural antioxidants PV and TBARS were retarded, especially in samples added with tannic acid (TA), catechin (CT) and gallic acid (GA) (p<0.05). Haem iron content decreased with increasing storage period and was found to be lower in samples added with caffeic acid (CA) and gallic acid (GA) at the end of storage period (p<0.05). Furthermore, lower mesophilic bacterial count (MBC) and psychrophilic bacterial counts (PBC) were observed in TA and CT treated samples compared to control and other samples (p<0.05). Camel meat treated with TA and CT also received higher likeness scores for colour, odor and overall appearance compared to control samples (p<0.05). Therefore, adding different natural antioxidants especially TA and CT showed retarding effect on lipid oxidation and microbial growth and were also effective in maintaining sensory attributes (color and odor) of ground camel meat during storage at 4°C. Hence, TA and CT could be considered as the potential natural antioxidant for preserving the quality of the camel meat displayed at refrigerated shelves.

Keywords: natural antioxidants, lipid oxidation, quality, camel meat

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Authors: Akwu N. A., Naidoo Y., Salau V. F., Olofinsan K. A.

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Grewia lasiocarpa E. Mey. ex Harv. (Malvaceae) is a Southern African medicinal plant indigenously used with other plants for birthing problems. The anti-diabetic properties of the hexane, chloroform, and methanol extracts of Grewia lasiocarpa stem bark were assessed using in vitro α-glucosidase enzyme inhibition assay. The predictive in silico drug-likeness and toxicity properties of the phytocompounds were conducted using the pKCSM, ADMElab, and SwissADME computer-aided online tools. The highest α-glucosidase percentage inhibition was observed in the hexane extract (86.76%, IC50= 0.24 mg/mL), followed by chloroform (63.08%, IC50= 4.87 mg/mL) and methanol (53.22%, IC50= 9.41 mg/mL); while acarbose, the standard anti-diabetic drug was (84.54%, IC50= 1.96 mg/mL). The α-glucosidase assay revealed that the hexane extract exhibited the strongest carbohydrate inhibiting capacity and is a better inhibitor than the standard reference drug-acarbose. The computational studies also affirm the results observed in the in vitroα-glucosidaseassay. Thus, the extracts of G. lasiocarpa may be considered a potential plant-sourced compound for treating type 2 diabetes mellitus. This is the first study on the anti-diabetic properties of Grewia lasiocarpa hexane, chloroform, and methanol extracts using in vitro and in silico models.

Keywords: grewia lasiocarpa, α-glucosidase inhibition, anti-diabetes, ADMET

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Authors: Sahana Selladurai, Christine DeWolf

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Lung surfactant comprises a lipid-protein film that coats the alveolar surface and serves to prevent alveolar collapse upon repeated breathing cycles. Exposure of lung surfactant to high concentrations of airborne pollutants, for example tropospheric ozone in smog, can chemically modify the lipid and protein components. These chemical changes can impact the film functionality by decreasing the film’s collapse pressure (minimum surface tension attainable), altering it is mechanical and flow properties and modifying lipid reservoir formation essential for re-spreading of the film during the inhalation process. In this study, we use Langmuir monolayers spread at the air-water interface as model membranes where the compression and expansion of the film mimics the breathing cycle. The impact of ozone exposure on model lung surfactant films is measured using a Langmuir film balance, Brewster angle microscopy and a pendant drop tensiometer as a function of film and sub-phase composition. The oxidized films are analyzed using mass spectrometry where lipid and protein oxidation products are observed. Oxidation is shown to reduce surface activity, alter line tension (and film morphology) and in some cases visibly reduce the viscoelastic properties of the film when compared to controls. These reductions in functionality of the films are highly dependent on film and sub-phase composition, where for example, the effect of oxidation is more pronounced when using a physiologically relevant buffer as opposed to water as the sub-phase. These findings can lead to a better understanding on the impact of continuous exposure to high levels of ozone on the mechanical process of breathing, as well as understanding the roles of certain lung surfactant components in this process.

Keywords: lung surfactant, oxidation, ozone, viscoelasticity

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Authors: Wadha Alqahtani

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In recent times, polymers have seen a great surge in interest in the field of medicine, particularly chemotherapeutics. One recent innovation is the conversion of polymeric materials into “polymeric nanoparticles”. These nanoparticles can be designed and modified to encapsulate and transport drugs selectively to cancer cells, minimizing collateral damage to surrounding healthy tissues, and improve patient quality of life. In this study, we have synthesized pseudo-branched polyester polymers from bio-based small molecules, including sorbitol, glutaric acid and a propargylic acid derivative to further modify the polymer to make it “click-able" with an azide-modified target ligand. Melt polymerization technique was used for this polymerization reaction, using lipase enzyme catalyst NOVO 435. This reaction was conducted between 90- 95 °C for 72 hours. The polymer samples were collected in 24-hour increments for characterization and to monitor reaction progress. The resulting polymer was purified with the help of methanol dissolving and filtering with filter paper then characterized via NMR, GPC, FTIR, DSC, TGA and MALDI-TOF. Following characterization, these polymers were converted to a polymeric nanoparticle drug delivery system using solvent diffusion method, wherein DiI optical dye and chemotherapeutic drug Taxol can be encapsulated simultaneously. The efficacy of the nanoparticle’s apoptotic effects were analyzed in-vitro by incubation with prostate cancer (LNCaP) and healthy (CHO) cells. MTT assays and fluorescence microscopy were used to assess the cellular uptake and viability of the cells after 24 hours at 37 °C and 5% CO2 atmosphere. Results of the assays and fluorescence imaging confirmed that the nanoparticles were successful in both selectively targeting and inducing apoptosis in 80% of the LNCaP cells within 24 hours without affecting the viability of the CHO cells. These results show the potential of using biodegradable polymers as a vehicle for receptor-specific drug delivery and a potential alternative for traditional systemic chemotherapy. Detailed experimental results will be discussed in the e-poster.

Keywords: chemotherapeutic drug, click chemistry, nanoparticle, prostat cancer

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Authors: Jyh J. Chen, Fu H. Yang, Ming H. Liao

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This study describes a capillary-based device integrated with the heating and cooling modules for polymerase chain reaction (PCR). The device consists of the reaction polytetrafluoroethylene (PTFE) capillary, the aluminum blocks, and is equipped with two cartridge heaters, a thermoelectric (TE) cooler, a fan, and some thermocouples for temperature control. The cartridge heaters are placed into the heating blocks and maintained at two different temperatures to achieve the denaturation and the extension step. Some thermocouples inserted into the capillary are used to obtain the transient temperature profiles of the reaction sample during thermal cycles. A 483-bp DNA template is amplified successfully in the designed system and the traditional thermal cycler. This work should be interesting to persons involved in the high-temperature based reactions and genomics or cell analysis.

Keywords: polymerase chain reaction, thermal cycles, capillary, TE cooler

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Authors: Wael A. Aboutaleb, Ahmed M. A. El Naggar, Heba M. Gobara

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This research work reports the photocatalytic production of hydrogen from water-methanol mixture using three different 15% ceria/iron oxide catalysts. The catalysts were prepared by physical mixing, precipitation, and ultrasonication methods and labeled as catalysts A-C. The structural and texture properties of the obtained catalysts were confirmed by X-ray diffraction (XRD), BET-surface area analysis and transmission electron microscopy (TEM). The photocatalytic activity of the three catalysts towards hydrogen generation was then tested. Promising hydrogen productivity was obtained by the three catalysts however different gases compositions were obtained by each type of catalyst. Specifically, catalyst A had produced hydrogen mixed with CO₂ while the composite structure (catalyst B) had generated only pure H₂. In the case of catalyst C, syngas made of H₂ and CO was revealed, as a novel product, for the first time, in such process.

Keywords: hydrogen production, water splitting, photocatalysts, clean energy

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Authors: Zhanat Shomanova, Ruslan Safarov, Yuri Nosenko, Zheneta Tashmuchambetova, Alima Zharmagambetova

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An effective way of utilization of ferroalloy production wastes is preparing hydrocarbon refining catalysts from them. It is possible due to accordable transition metals containing in the wastes. In the work, we are presenting the results on elemental analysis of sludge samples from Aksu ferroalloy plant (Aksu, Kazakhstan), method of catalysts preparing, results of physical-chemical analysis of obtained catalysts (X-ray analysis, electron microscopy, the BET method etc.), results of using the catalysts in some hydrocarbons refining processes such as hydrocracking of rubber waste, cracking of gasoil, oxidation of cyclohexane. The main results of catalytic activity research are: a) In hydrocracking of rubber waste 64.9% of liquid products were fuel fractions; b) In cracking of gasoil conversion was 51% and selectivity by liquid products was 99%; c) In oxidation of cyclohexane the maximal product yield 87.9% and selectivity by cyclohexanol 93.0% were achieved.

Keywords: catalyst, cyclohexane oxidation, ferroalloy production waste, gasoil cracking

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Authors: Malee Santikunaporn, Neera Wongtyanuwat, Channarong Asavatesanupap

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Pyrolysis of waste oil is an effective process to produce high quality liquid fuels. In this work, pyrolysis experiments of waste oil over Y zeolite were carried out in a semi-batch reactor under a flow of nitrogen at atmospheric pressure and at different reaction temperatures (350-450 ^oC). The products were gas, liquid fuel, and residue. Only liquid fuel was further characterized for its composition and properties by using gas chromatography, thermogravimetric analyzer, and bomb calorimeter. Experimental results indicated that the pyrolysis reaction temperature significantly affected both yield and composition distribution of pyrolysis oil. An increase in reaction temperature resulted in increased fuel yield, especially gasoline fraction. To obtain high amount of fuel, the optimal reaction temperature should be higher than 350 ^oC. A presence of Y zeolite in the system enhanced the cracking activity. In addition, the pyrolysis oil yield is proportional to the catalyst quantity.

Keywords: gasoline, diesel, pyrolysis, waste oil, Y zeolite

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Authors: Kanda Wongwailikhit

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Copper (I) oxide microparticles with the morphology of cubic and hollow sphere were synthesized with the assistance of a surfactant as the shape controller. Both particles were then subjected to a study of the catalytic activity and the results of shape effects of catalysts on rate of catalytic reaction was observed. The decolorizing reaction of crystal violet and sodium hydroxide was chosen and the decrease of reactant with respect to time was measured using a spectrophotometer. The result revealed that morphology of the crystal had no effect on the catalytic activity for the crystal violet reaction but contributed to total surface area predominantly.

Keywords: copper (I) oxide, catalytic activity, crystal violet

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Authors: Manjusha C. Padole, Parag A. Deshpande

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Density functional theory calculations were carried out for identification of an active heterogeneous catalyst to carry out Heck coupling reaction which is of pharmaceutical importance. One of the carbonaceous nanomaterials, heterofullerene, was designed for the reaction. Stability and reactivity of the proposed heterofullerenes (C59M, M = Pd/Ni) were established with insights into the metal-carbon bond, electron affinity and chemical potential. Adsorbent potentials of both the heterofullerenes were examined from the adsorption study of four halobenzenes (C6H5F, C6H5Cl, C6H5Br and C6H5I). Oxidative addition activities of all four halobenzenes were investigated by developing free energy landscapes over both the heterofullerenes for rate determining step (oxidative addition). C6H5I showed a good catalytic activity for the rate determining step. Thus, C6H5I was proposed as a suitable halobenzene and complete free energy landscapes for Heck coupling reaction were developed over C59Pd and C59Ni. Smaller activation barriers observed over C59Pd in comparison with C59Ni put us in a position to propose C59Pd to be an efficient heterofullerene for carrying Heck coupling reaction.

Keywords: metal-substituted fullerene, density functional theory, electron affinity, oxidative addition, Heck coupling reaction

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Authors: Juree Hong, Sanggeun Lee, Jungmok Seo, Taeyoon Lee

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We report a facile synthesis of metal nano particles (NPs) on graphene layer via galvanic displacement reaction between graphene-buffered copper (Cu) and metal ion-containing salts. Diverse metal NPs can be formed on graphene surface and their morphologies can be tailored by controlling the concentration of metal ion-containing salt and immersion time. The obtained metal NP-decorated single-layer graphene (SLG) has been used as hydrogen gas (H2) sensing material and exhibited highly sensitive response upon exposure to 2% of H2.

Keywords: metal nanoparticle, galvanic displacement reaction, graphene, hydrogen sensor

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Authors: A. Benhadji, M. Taleb Ahmed

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Among the various methods of treatment, advanced oxidation processes (AOP) are the most promising ones. In this study, Peroxi Electrocoagulation Process (PEP) was investigated for the treatment of detergent wastewater. The process was compared with electrooxidation treatment. The results showed that chemical oxygen demand (COD) was high 7584 mgO₂.L^-1, while the biochemical oxygen demand was low (250 mgO₂.L^-1). This wastewater was hardly biodegradable. Electrochemical process was carried out for the removal of detergent using a glass reactor with a volume of 1 L and fitted with three electrodes. A direct current (DC) supply was used. Samples were taken at various current density (0.0227 A/cm² to 0.0378 A/cm²) and reaction time (1-2-3-4 and 5 hour). Finally, the COD was determined. The results indicated that COD removal efficiency of PEP was observed to increase with current intensity and reached to 77% after 5 h. The highest removal efficiency was observed after 5 h of treatment.

Keywords: AOP, COD, detergent, PEP, wastewater

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Authors: Raphaelle Guillou, Matthieu Le Saux, Jean-Christophe Brachet, Thomas Guilbert, Elodie Rouesne, Denis Menut, Caroline Toffolon-Masclet, Dominique Thiaudiere

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In some hypothetical accidental situations, such as during a Loss Of Coolant Accident (LOCA) in pressurized water reactors, fuel cladding tubes made of zirconium alloys can be exposed for a few minutes to steam at High Temperature (HT up to 1200°C) before being cooled and then quenched in water. Under LOCA-like conditions, the cladding undergoes a number of metallurgical changes (phase transformations, oxygen diffusion and growth of an oxide layer...) and is consequently submitted to internal stresses whose state evolves during the transient. These stresses can have an effect on the oxide structure and the oxidation kinetics of the material. They evolve during cooling, owing to differences between the thermal expansion coefficients of the various phases and phase transformations of the metal and the oxide. These stresses may result in the failure of the cladding during quenching, once the material is embrittled by oxidation. In order to progress in the evaluation of these internal stresses, X-ray diffraction experiments were performed in-situ under synchrotron radiation during HT oxidation and subsequent cooling on Zircaloy-4 sheet samples. First, structural evolutions, such as phase transformations, have been studied as a function of temperature for both the oxide layer and the metallic substrate. Then, internal stresses generated within the material oxidized at temperatures between 700 and 900°C have been evaluated thanks to the 2θ diffraction peak position shift measured during the in-situ experiments. Electron backscatter diffraction (EBSD) analysis was performed on the samples after cooling in order to characterize their crystallographic texture. Furthermore, macroscopic strains induced by oxidation in the conditions investigated during the in-situ X-ray diffraction experiments were measured in-situ in a dilatometer.

Keywords: APRP, stains measurements, synchrotron diffraction, zirconium allows

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Authors: Miguel A. Figueroa, José A. Lara-Ramos, Miguel A. Mueses

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Pharmaceutical residues are a section of emerging contaminants of anthropogenic origin that are present in a myriad of waters with which human beings interact daily and are starting to affect the ecosystem directly. Conventional waste-water treatment systems are not capable of degrading these pharmaceutical effluents because their designs cannot handle the intermediate products and biological effects occurring during its treatment. That is why it is necessary to hybridize conventional waste-water systems with non-conventional processes. In the specific case of an ozonation process, its efficiency highly depends on a perfect dispersion of ozone, long times of interaction of the gas-liquid phases and the size of the ozone bubbles formed through-out the reaction system. In order to increase the efficiency of these parameters, the use of a modified flotation cell has been proposed recently as a reactive system, which is used at an industrial level to facilitate the suspension of particles and spreading gas bubbles through the reactor volume at a high rate. The objective of the present work is the development of a mathematical model that can closely predict the kinetic rates of reactions taking place in the flotation cell at an experimental scale by means of identifying proper reaction mechanisms that take into account the modified chemical and hydrodynamic factors in the FeO-catalyzed Ozonation of Diclofenac aqueous solutions in a flotation cell. The methodology is comprised of three steps: an experimental phase where a modified flotation cell reactor is used to analyze the effects of ozone concentration and loading catalyst over the degradation of Diclofenac aqueous solutions. The performance is evaluated through an index of utilized ozone, which relates the amount of ozone supplied to the system per milligram of degraded pollutant. Next, a theoretical phase where the reaction mechanisms taking place during the experiments must be identified and proposed that details the multiple direct and indirect reactions the system goes through. Finally, a kinetic model is obtained that can mathematically represent the reaction mechanisms with adjustable parameters that can be fitted to the experimental results and give the model a proper physical meaning. The expected results are a robust reaction rate law that can simulate the improved results of Diclofenac mineralization on water using the modified flotation cell reactor. By means of this methodology, the following results were obtained: A robust reaction pathways mechanism showcasing the intermediates, free-radicals and products of the reaction, Optimal values of reaction rate constants that simulated Hatta numbers lower than 3 for the system modeled, degradation percentages of 100%, TOC (Total organic carbon) removal percentage of 69.9 only requiring an optimal value of FeO catalyst of 0.3 g/L. These results showed that a flotation cell could be used as a reactor in ozonation, catalytic ozonation and photocatalytic ozonation processes, since it produces high reaction rate constants and reduces mass transfer limitations (Ha > 3) by producing microbubbles and maintaining a good catalyst distribution.

Keywords: advanced oxidation technologies, iron oxide, emergent contaminants, AOTS intensification

Procedia PDF Downloads 107

Authors: Tânia F. C. V. Silva, Eloísa S. S. Vieira, João Pinto da Costa, Rui A. R. Boaventura, Vitor J. P. Vilar

Abstract:

Sanitary landfill leachates are characterized as a complex mixture of diverse organic and inorganic contaminants, which are usually removed by combining different treatment processes. Due to its simplicity, reliability, high cost-effectiveness and high nitrogen content (mostly under the ammonium form) inherent in this type of effluent, the activated sludge biological process is almost always applied in leachate treatment plants (LTPs). The purpose of this work is to assess the effect of the main nitrification and denitrification variables on the nitrogen's biological removal, from mature leachates. The leachate samples were collected after an aerated lagoon, at a LTP nearby Porto, presenting a high amount of dissolved organic carbon (1.0-1.3 g DOC/L) and ammonium nitrogen (1.1-1.7 g NH4+-N/L). The experiments were carried out in a 1-L lab-scale batch reactor, equipped with a pH, temperature and dissolved oxygen (DO) control system, in order to determine the reaction kinetic constants at unchanging conditions. The nitrification reaction rate was evaluated while varying the (i) operating temperature (15, 20, 25 and 30ºC), (ii) DO concentration interval (0.5-1.0, 1.0-2.0 and 2.0-4.0 mg/L) and (iii) solution pH (not controlled, 7.5-8.5 and 6.5-7.5). At the beginning of most assays, it was verified that the ammonium stripping occurred simultaneously to the nitrification, reaching up to 37% removal of total dissolved nitrogen. The denitrification kinetic constants and the methanol consumptions were calculated for different values of (i) volatile suspended solids (VSS) content (25, 50 and 100 mL of centrifuged sludge in 1 L solution), (ii) pH interval (6.5-7.0, 7.5-8.0 and 8.5-9.0) and (iii) temperature (15, 20, 25 and 30ºC), using effluent previously nitrified. The maximum nitrification rate obtained was 38±2 mg NH4+-N/h/g VSS (25ºC, 0.5-1.0 mg O2/L, pH not controlled), consuming 4.4±0.3 mg CaCO3/mg NH4+-N. The highest denitrification rate achieved was 19±1 mg (NO2--N+NO3--N)/h/g VSS (30ºC, 50 mL of sludge and pH between 7.5 and 8.0), with a C/N consumption ratio of 1.1±0.1 mg CH3OH/mg (NO2--N+NO3--N) and an overall alkalinity production of 3.7±0.3 mg CaCO3/mg (NO2--N+NO3--N). The denitrification process showed to be sensitive to all studied parameters, while the nitrification reaction did not suffered significant change when DO content was changed.

Keywords: mature sanitary landfill leachate, nitrogen removal, nitrification and denitrification parameters, lab-scale activated sludge biological reactor

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Authors: S. Said, Asmaa A. Abdulrahman

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MoOₓ/Al₂O₃ based catalyst has long been widely used as an active catalyst in oxidative desulfurization reaction due to its high stability under severe reaction conditions and high resistance to sulfur poisoning. In this context, 4 & 9wt.% MoO₃ grafted on mesoporous γ-Al₂O₃ has been synthesized using the modified atomic layer deposition (ALD) method. Another MoO₃/Al₂O₃ sample was prepared by the conventional wetness impregnation (IM) method, for comparison. The effect of the preparation methods on the metal-support interaction was evaluated using different characterization techniques, including X-ray diffraction, X-ray photoelectron spectroscopy (XPS), N₂-physisorption, transmission electron microscopy (TEM), H₂- temperature-programmed reduction and FT-IR. Oxidative desulfurization (ODS) reaction of the model fuel oil was used as a probe reaction to examine the catalytic efficiency of the prepared catalysts. ALD method led to samples with much better physicochemical properties than those of the prepared one via the impregnation method. However, the 9 wt.%MoO₃/Al₂O₃ (ALD) catalyst in the ODS reaction of model fuel oil shows enhanced catalytic performance with ~90%, which has been attributed to the more Mo⁶⁺ surface concentrations relative to Al³⁺ with large pore diameter and surface area. The kinetic study shows that the ODS of DBT follows a pseudo first-order rate reaction.

Keywords: mesoporous Al₂O₃, xMoO₃/Al₂O₃, atomic layer deposition, wetness impregnation, ODS, DBT

Procedia PDF Downloads 98

Authors: C. N. Okafor, M. Maaza, T. A. E. Mokrani

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A proton exchange membrane has been developed for Direct Methanol Fuel Cell (DMFC). The nanofiber network composite membranes were prepared by interconnected network of Nafion (perfuorosulfonic acid) nanofibers that have been embedded in an uncharged and inert polymer matrix, by electro-spinning. The spinning solution of Nafion with a low concentration (1 wt. % compared to Nafion) of high molecular weight poly(ethylene oxide), as a carrier polymer. The interconnected network of Nafion nanofibers with average fiber diameter in the range of 160-700nm, were used to make the membranes, with the nanofiber occupying up to 85% of the membrane volume. The matrix polymer was cross-linked with Norland Optical Adhesive 63 under UV. The resulting membranes showed proton conductivity of 0.10 S/cm at 25°C and 80% RH; and methanol permeability of 3.6 x 10-6 cm2/s.

Keywords: composite membrane, electrospinning, fuel cell, nanofibers

Procedia PDF Downloads 258

Authors: N. Naga Subrahmanyeswara Rao, Parag Arvind Deshpande

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Understanding nucleotide synthesis reaction of any organism is beneficial to know the growth of it as in Mycobacterium tuberculosis to design anti TB drug. One of the reactions of de novo pathway which takes place in all organisms was considered. The reaction takes places between phosphoribosyl pyrophosphate and orotate catalyzed by orotate phosphoribosyl transferase and divalent metal ion gives orotdine monophosphate, a nucleotide. All the reaction steps of three experimentally proposed mechanisms for this reaction were considered to develop kinetic rate expression. The model was validated using the data for four organisms. This model could successfully describe the kinetics for the reported data. The developed model can serve as a reliable model to describe the kinetics in new organisms without the need of mechanistic determination. So an organism-independent model was developed.

Keywords: mechanism, nucleotide, organism, tuberculosis

Procedia PDF Downloads 326

Authors: Hernan Arturo Blas López, Gustavo Henndel Lopes, Antonio Carlos Silva Costa Teixeira, Carmen Elena Flores Barreda, Patricia Araujo Pantoja

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Phenols are toxic for life and the environment and may come from many sources. Uncured phenolic monomers present in phenolic resins used as binders in grinding wheels and emery paper can contaminate industrial wastewaters in abrasives manufacture plants. Furthermore, vestiges of resol and novolacs resins generated by wear and tear of abrasives are also possible sources of water contamination by phenolics in these facilities. Fortunately, advanced oxidation by dark Fenton and photo-Fenton techniques are capable of oxidizing phenols and their degradation products up to their mineralization into H₂O and CO₂. The maximal allowable concentrations for phenols in Peruvian waterbodies is very low, such that insufficiently treated effluents from the abrasives industry are a potential environmental noncompliance. The current case study highlights findings obtained during the lab-scale application of Fenton’s and photo-assisted Fenton’s chemistries to real industrial wastewater samples from an abrasives manufacture plant in Peru. The goal was to reduce the phenolic content and sample toxicity. For this purpose, two independent variables-reaction time and effect of ultraviolet radiation–were studied as for their impacts on the concentration of total phenols, total organic carbon (TOC), biological oxygen demand (BOD) and chemical oxygen demand (COD). In this study, diluted samples (1 L) of the industrial effluent were treated with Fenton’s reagent (H₂O₂ and Fe²⁺ from FeSO₄.H₂O) during 10 min in a photochemical batch reactor (Alphatec RFS-500, Brazil) at pH 2.92. In the case of photo-Fenton tests with ultraviolet lamps of 9 W, UV-A, UV-B and UV-C lamps were evaluated. All process conditions achieved 100% of phenols degraded within 5 minutes. TOC, BOD and COD decreased by 49%, 52% and 86% respectively (all processes together). However, Fenton treatment was not capable of reducing BOD, COD and TOC below a certain value even after 10 minutes, contrarily to photo-Fenton. It was also possible to conclude that the processes here studied degrade other compounds in addition to phenols, what is an advantage. In all cases, elevated effluent dilution factors and high amounts of oxidant agent impact negatively the overall economy of the processes here investigated.

Keywords: fenton oxidation, wastewater treatment, phenols, abrasives industry

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Authors: Ane Larrea, Victor Sebastian, Manuel Arruebo, Jesus Santamaria

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We present a gas-liquid microfluidic system as a reactor to obtain magnetite nanoparticles with an excellent degree of control regarding their crystalline phase, shape and size. Several types of microflow approaches were selected to prevent nanomaterial aggregation and to promote homogenous size distribution. The selected reactor consists of a mixer stage aided by ultrasound waves and a reaction stage using a N2-liquid segmented flow to prevent magnetite oxidation to non-magnetic phases. A milli-fluidic reactor was developed to increase the production rate where a magnetite throughput close to 450 mg/h in a continuous fashion was obtained.

Keywords: continuous production, magnetic nanoparticles, microfluidics, nanomaterials

Procedia PDF Downloads 582