Search results for: hydrogen adsorption

Authors: D. Malouch, M. Berchel, C. Dreanno, S. Stachowski-Haberkorn, P-A. Jaffres

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Biofouling is a complex natural phenomenon that involves biological, physical and chemical properties related to the environment, the submerged surface and the living organisms involved. Bio-colonization of artificial structures can cause various economic and environmental impacts. The increase in costs associated with the over-consumption of fuel from biocolonized vessels has been widely studied. Measurement drifts from submerged sensors, as well as obstructions in heat exchangers, and deterioration of offshore structures are major difficulties that industries are dealing with. Therefore, surfaces that inhibit biocolonization are required in different areas (water treatment, marine paints, etc.) and many efforts have been devoted to produce efficient and eco-compatible antifouling agents. The different steps of surface fouling are widely described in literature. Studying the biofilm and its stages provides a better understanding of how to elaborate more efficient antifouling strategies. Several approaches are currently applied, such as the use of biocide anti-fouling paint (mainly with copper derivatives) and super-hydrophobic coatings. While these two processes are proving to be the most effective, they are not entirely satisfactory, especially in a context of a changing legislation. Nowadays, the challenge is to prevent biofouling with non-biocide compounds, offering a cost effective solution, but with no toxic effects on marine organisms. Since the micro-fouling phase plays an important role in the regulation of the following steps of biofilm formation, it is desired to reduce or delate biofouling of a given surface by inhibiting the micro-fouling at its early stages. In our recent works, we reported that some amphiphilic compounds exhibited bacteriostatic or bactericidal properties at a concentration that did not affect mammalian eukaryotic cells. These remarkable properties invited us to assess this type of bio-inspired phospholipids to prevent the colonization of surfaces by marine bacteria. Of note, other studies reported that amphiphilic compounds interacted with bacteria leading to a reduction of their development. An amphiphilic compound is a molecule consisting of a hydrophobic domain and a polar head (ionic or non-ionic). These compounds appear to have interesting antifouling properties: some ionic compounds have shown antimicrobial activity, and zwitterions can reduce nonspecific adsorption of proteins. Herein, we investigate the potential of amphiphilic compounds as inhibitors of bacterial growth and marine biofilm formation. The aim of this study is to compare the efficacy of four synthetic phospholipids that features a cationic charge or a zwitterionic polar-head group to prevent microfouling with marine bacteria. Toxicity of these compounds was also studied in order to identify the most promising compounds that inhibit biofilm development and show low cytotoxicity on two links representative of coastal marine food webs: phytoplankton and oyster larvae.

Keywords: amphiphilic phospholipids, biofilm, marine fouling, non-toxique assays

Procedia PDF Downloads 112

Authors: Alberto Veses, Olga Sanhauja, María Soledad Callén, Tomás García

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The appropriate use of renewable sources emerges as a decisive point to minimize the environmental impact caused by fossil fuels use. Particularly, the use of lignocellulosic biomass becomes one of the best promising alternatives since it is the only carbon-containing renewable source that can produce bioproducts similar to fossil fuels and it does not compete with food market. Among all the processes that can valorize lignocellulosic biomass, pyrolysis is an attractive alternative because it is the only thermochemical process that can produce a liquid biofuel (bio-oil) in a simple way and solid and gas fractions that can be used as energy sources to support the process. However, in order to incorporate bio-oils in current infrastructures and further process in future biorefineries, their quality needs to be improved. Introducing different low-cost catalysts and/or incorporating different polymer residues to the process are some of the new, simple and low-cost strategies that allow the user to directly obtain advanced bio-oils to be used in future biorefineries in an economic way. In this manner, from previous thermogravimetric analyses, local agricultural wastes such as grape seeds (GS) were selected as lignocellulosic biomass while, waste tires (WT) were selected as polymer residue. On the other hand, CaO was selected as low-cost catalyst based on previous experiences by the group. To reach this aim, a specially-designed fixed bed reactor using N₂ as a carrier gas was used. This reactor has the peculiarity to incorporate a vertical mobile liner that allows the user to introduce the feedstock in the oven once the selected temperature (550 ºC) is reached, ensuring higher heating rates needed for the process. Obtaining a well-defined phase distribution in the resulting bio-oil is crucial to ensure the viability to the process. Thus, once experiments were carried out, not only a well-defined two layers was observed introducing several mixtures (reaching values up to 40 wt.% of WT) but also, an upgraded organic phase, which is the one considered to be processed in further biorefineries. Radical interactions between GS and WT released during the pyrolysis process and dehydration reactions enhanced by CaO can promote the formation of better-quality bio-oils. The latter was reflected in a reduction of water and oxygen content of bio-oil and hence, a substantial increase of its heating value and its stability. Moreover, not only sulphur content was reduced from solely WT pyrolysis but also potential and negative issues related to a strong acidic environment of conventional bio-oils were minimized due to its basic pH and lower total acid numbers. Therefore, acidic compounds obtained in the pyrolysis such as CO₂-like substances can react with the CaO and minimize acidic problems related to lignocellulosic bio-oils. Moreover, this CO₂ capture promotes H₂ production from water gas shift reaction favoring hydrogen-transfer reactions, improving the final quality of the bio-oil. These results show the great potential of grapes seeds to carry out the catalytic co-pyrolysis process with different plastic residues in order to produce a liquid bio-oil that can be considered as a high-quality renewable vector.

Keywords: advanced bio-oils, biorefinery, catalytic co-pyrolysis of biomass and waste tires, lignocellulosic biomass

Procedia PDF Downloads 210

Authors: Marta Paszkiewicz, Justyna Łuczak, Martyna Marchelek, Adriana Zaleska-Medynska

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In recent years, photocatalytical processes have been intensively investigated for destruction of pollutants, hydrogen evolution, disinfection of water, air and surfaces, for the construction of self-cleaning materials (tiles, glass, fibres, etc.). Titanium dioxide (TiO2) is the most popular material used in heterogeneous photocatalysis due to its excellent properties, such as high stability, chemical inertness, non-toxicity and low cost. It is well known that morphology and microstructure of TiO2 significantly influence the photocatalytic activity. This characteristics as well as other physical and structural properties of photocatalysts, i.e., specific surface area or density of crystalline defects, could be controlled by preparation route. In this regard, TiO2 particles can be obtained by sol-gel, hydrothermal, sonochemical methods, chemical vapour deposition and alternatively, by ionothermal synthesis using ionic liquids (ILs). In the TiO2 particles synthesis ILs may play a role of a solvent, soft template, reagent, agent promoting reduction of the precursor or particles stabilizer during synthesis of inorganic materials. In this work, the effect of the ILs anion type on morphology and photoactivity of TiO2 is presented. The preparation of TiO2 microparticles with spherical structure was successfully achieved by solvothermal method, using tetra-tert-butyl orthotitatane (TBOT) as the precursor. The reaction process was assisted by an ionic liquids 1-butyl-3-methylimidazolium bromide [BMIM][Br], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium haxafluorophosphate [BMIM][PF6]. Various molar ratios of all ILs to TBOT (IL:TBOT) were chosen. For comparison, reference TiO2 was prepared using the same method without IL addition. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brenauer-Emmett-Teller surface area (BET), NCHS analysis, and FTIR spectroscopy were used to characterize the surface properties of the samples. The photocatalytic activity was investigated by means of phenol photodegradation in the aqueous phase as a model pollutant, as well as formation of hydroxyl radicals based on detection of fluorescent product of coumarine hydroxylation. The analysis results showed that the TiO2 microspheres had spherical structure with the diameters ranging from 1 to 6 µm. The TEM micrographs gave a bright observation of the samples in which the particles were comprised of inter-aggregated crystals. It could be also observed that the IL-assisted TiO2 microspheres are not hollow, which provides additional information about possible formation mechanism. Application of the ILs results in rise of the photocatalytic activity as well as BET surface area of TiO2 as compared to pure TiO2. The results of the formation of 7-hydroxycoumarin indicated that the increased amount of ·OH produced at the surface of excited TiO2 for samples TiO2_ILs well correlated with more efficient degradation of phenol. NCHS analysis showed that ionic liquids remained on the TiO2 surface confirming structure directing role of that compounds.

Keywords: heterogeneous photocatalysis, IL-assisted synthesis, ionic liquids, TiO2

Procedia PDF Downloads 243

Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

Procedia PDF Downloads 238

Authors: Heather Mroz

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Geothermal fluids can provide a nearly unlimited source of renewable energy but are often highly corrosive due to dissolved carbon dioxide (CO2), hydrogen sulphide (H2S), Ammonia (NH3) and chloride ions. The corrosive environment drives material selection for many components, including piping, heat exchangers and pressure vessels, to higher alloys of stainless steel, nickel-based alloys and titanium. The use of these alloys is cost-prohibitive and does not offer the pressure rating of carbon steel. One solution, explosion cladding, has been proven to reduce the capital cost of the geothermal equipment while retaining the mechanical and corrosion properties of both the base metal and the cladded surface metal. Explosion cladding is a solid-state welding process that uses precision explosions to bond two dissimilar metals while retaining the mechanical, electrical and corrosion properties. The process is commonly used to clad steel with a thin layer of corrosion-resistant alloy metal, such as stainless steel, brass, nickel, silver, titanium, or zirconium. Additionally, explosion welding can join a wider array of compatible and non-compatible metals with more than 260 metal combinations possible. The explosion weld is achieved in milliseconds; therefore, no bulk heating occurs, and the metals experience no dilution. By adhering to a strict set of manufacturing requirements, both the shear strength and tensile strength of the bond will exceed the strength of the weaker metal, ensuring the reliability of the bond. For over 50 years, explosion cladding has been used in the oil and gas and chemical processing industries and has provided significant economic benefit in reduced maintenance and lower capital costs over solid construction. The focus of this paper will be on the many benefits of the use of explosion clad in process equipment instead of more expensive solid alloy construction. The method of clad-plate production with explosion welding as well as the methods employed to ensure sound bonding of the metals. It will also include the origins of explosion cladding as well as recent technological developments. Traditionally explosion clad plate was formed into vessels, tube sheets and heads but recent advances include explosion welded piping. The final portion of the paper will give examples of the use of explosion-clad metals in geothermal energy recovery. The classes of materials used for geothermal brine will be discussed, including stainless steels, nickel alloys and titanium. These examples will include heat exchangers (tube sheets), high pressure and horizontal separators, standard pressure crystallizers, piping and well casings. It is important to educate engineers and designers on material options as they develop equipment for geothermal resources. Explosion cladding is a niche technology that can be successful in many situations, like geothermal energy recovery, where high temperature, high pressure and corrosive environments are typical. Applications for explosion clad metals include vessel and heat exchanger components as well as piping.

Keywords: clad metal, explosion welding, separator material, well casing material, piping material

Procedia PDF Downloads 134

Authors: Päärn Paiste, Margit Kõiv, Riho Mõtlep, Kalle Kirsimäe

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For small-scale wastewater management, the treatment wetlands (TWs) as a low cost alternative to conventional treatment facilities, can be used. However, P removal capacity of TW systems is usually problematic. P removal in TWs is mainly dependent on the physico–chemical and hydrological properties of the filter material. Highest P removal efficiency has been shown trough Ca-phosphate precipitation (i.e. active filtration) in Ca-rich alkaline filter materials, e.g. industrial by-products like hydrated oil shale ash (HOSA), metallurgical slags. In this contribution we report preliminary results of a full-scale TW system using HOSA material for P removal for a municipal wastewater at Nõo site, Estonia. The main goals of this ongoing project are to evaluate: a) the long-term P removal efficiency of HOSA using real waste water; b) the effect of high organic loading rate; c) variable P-loading effects on the P removal mechanism (adsorption/direct precipitation); and d) the form and composition of phosphate precipitates. Onsite full-scale experiment with two concurrent filter systems for treatment of municipal wastewater was established in September 2013. System’s pretreatment steps include septic tank (2 m2) and vertical down-flow LECA filters (3 m2 each), followed by horizontal subsurface HOSA filters (effective volume 8 m3 each). Overall organic and hydraulic loading rates of both systems are the same. However, the first system is operated in a stable hydraulic loading regime and the second in variable loading regime that imitates the wastewater production in an average household. Piezometers for water and perforated sample containers for filter material sampling were incorporated inside the filter beds to allow for continuous in-situ monitoring. During the 18 months of operation the median removal efficiency (inflow to outflow) of both systems were over 99% for TP, 93% for COD and 57% for TN. However, we observed significant differences in the samples collected in different points inside the filter systems. In both systems, we observed development of preferred flow paths and zones with high and low loadings. The filters show formation and a gradual advance of a “dead” zone along the flow path (zone with saturated filter material characterized by ineffective removal rates), which develops more rapidly in the system working under variable loading regime. The formation of the “dead” zone is accompanied by the growth of organic substances on the filter material particles that evidently inhibit the P removal. Phase analysis of used filter materials using X-ray diffraction method reveals formation of minor amounts of amorphous Ca-phosphate precipitates. This finding is supported by ATR-FTIR and SEM-EDS measurements, which also reveal Ca-phosphate and authigenic carbonate precipitation. Our first experimental results demonstrate that organic pollution and loading regime significantly affect the performance of hydrated ash filters. The material analyses also show that P is incorporated into a carbonate substituted hydroxyapatite phase.

Keywords: active filtration, apatite, hydrated oil shale ash, organic pollution, phosphorus

Procedia PDF Downloads 249

Authors: T. P. Sathishkumar, P. Navaneethakrishnan

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The research work investigates the variation of tensile properties for the sansevieria ehrenbergii fiber (SEF) and SEF reinforced polyester composites respect to various water absorption time. The experiments were conducted according to ATSM D3379-75 and ASTM D570 standards. The percentage of water absorption for composite specimens was measured according to ASTM D570 standard. The fiber of SE was cut in to 30 mm length for preparation of the composites. The simple hand lay-up method followed by compression moulding process adopted to prepare the randomly oriented SEF reinforced polyester composites at constant fiber weight fraction of 40%. The surface treatment was done on the SEFs with various chemicals such as NaOH, KMnO4, Benzoyl Peroxide, Benzoyl Chloride and Stearic Acid before preparing the composites. NaOH was used for pre-treatment of all other chemical treatments. The morphology of the tensile fractured specimens studied using the Scanning Electron Microscopic. The tensile strength of the SEF and SEF reinforced polymer composites were carried out with various water absorption time such as 4, 8, 12, 16, 20 and 24 hours respectively. The result shows that the tensile strength was drop off with increase in water absorption time for all composites. The highest tensile property of raw fiber was found due to lowest moistures content. Also the chemical bond between the cellulose and cementic materials such as lignin and wax was highest due to lowest moisture content. Tensile load was lowest and elongation was highest for the water absorbed fibers at various water absorption time ranges. During this process, the fiber cellulose inhales the water and expands the primary and secondary fibers walls. This increases the moisture content in the fibers. Ultimately this increases the hydrogen cation and the hydroxide anion from the water. In tensile testing, the water absorbed fibers shows highest elongation by stretching of expanded cellulose walls and the bonding strength between the fiber cellulose is low. The load carrying capability was stable at 20 hours of water absorption time. This could be directly affecting the interfacial bonding between the fiber/matrix and composite strength. The chemically treated fibers carry higher load and lower elongation which is due to removal of lignin, hemicellulose and wax content. The water time absorption decreases the tensile strength of the composites. The chemically SEF reinforced composites shows highest tensile strength compared to untreated SEF reinforced composites. This was due to highest bonding area between the fiber/matrix. This was proven in the morphology at the fracture zone of the composites. The intra-fiber debonding was occurred by water capsulation in the fiber cellulose. Among all, the tensile strength was found to be highest for KMnO4 treated SEF reinforced composite compared to other composites. This was due to better interfacial bonding between the fiber-matrix compared to other treated fiber composites. The percentage of water absorption of composites increased with time of water absorption. The percentage weight gain of chemically treated SEF composites at 4 hours to zero water absorption are 9, 9, 10, 10.8 and 9.5 for NaOH, BP, BC, KMnO4 and SA respectively. The percentage weight gain of chemically treated SEF composites at 24 hours to zero water absorption 5.2, 7.3, 12.5, 16.7 and 13.5 for NaOH, BP, BC, KMnO4 and SA respectively. Hence the lowest weight gain was found for KMnO4 treated SEF composites by highest percentage with lowest water uptake. However the chemically treated SEF reinforced composites is possible materials for automotive application like body panels, bumpers and interior parts, and household application like tables and racks etc.

Keywords: fibres, polymer-matrix composites (PMCs), mechanical properties, scanning electron microscopy (SEM)

Procedia PDF Downloads 388

Authors: Seema Kothari, Dinesh Panday

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An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

Procedia PDF Downloads 309

Authors: Helen S. Joyner (Melito), Mohammad Anvari

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Concentrated emulsions stabilized by proteins are systems of great importance in food, pharmaceutical and cosmetic products. Controlling emulsion rheology is critical for ensuring desired properties during formation, storage, and consumption of emulsion-based products. Studies on concentrated emulsions have focused on rheology of monodispersed systems. However, emulsions used for industrial applications are polydispersed in nature, and this polydispersity is regarded as an important parameter that also governs the rheology of the concentrated emulsions. Therefore, the objective of this study was to characterize rheological (small and large deformation behaviors) and microstructural properties of concentrated emulsions which were not truly monodispersed as usually encountered in food products such as margarines, mayonnaise, creams, spreads, and etc. The concentrated emulsions were prepared at different concentrations of fish gelatin (0.2, 0.4, 0.8% w/v in the whole emulsion system), oil-water ratio 80-20 (w/w), homogenization speed 10000 rpm, and 25oC. Confocal laser scanning microscopy (CLSM) was used to determine the microstructure of the emulsions. To prepare samples for CLSM analysis, FG solutions were stained by Fluorescein isothiocyanate dye. Emulsion viscosity profiles were determined using shear rate sweeps (0.01 to 100 1/s). The linear viscoelastic regions (LVRs) of the emulsions were determined using strain sweeps (0.01 to 100% strain) for each sample. Frequency sweeps were performed in the LVR (0.1% strain) from 0.6 to 100 rad/s. Large amplitude oscillatory shear (LAOS) testing was conducted by collecting raw waveform data at 0.05, 1, 10, and 100% strain at 4 different frequencies (0.5, 1, 10, and 100 rad/s). All measurements were performed in triplicate at 25oC. The CLSM results revealed that increased fish gelatin concentration resulted in more stable oil-in-water emulsions with homogeneous, finely dispersed oil droplets. Furthermore, the protein concentration had a significant effect on emulsion rheological properties. Apparent viscosity and dynamic moduli at small deformations increased with increasing fish gelatin concentration. These results were related to increased inter-droplet network connections caused by increased fish gelatin adsorption at the surface of oil droplets. Nevertheless, all samples showed shear-thinning and weak gel behaviors over shear rate and frequency sweeps, respectively. Lissajous plots, or plots of stress versus strain, and phase lag values were used to determine nonlinear behavior of the emulsions in LAOS testing. Greater distortion in the elliptical shape of the plots followed by higher phase lag values was observed at large strains and frequencies in all samples, indicating increased nonlinear behavior. Shifts from elastic-dominated to viscous dominated behavior were also observed. These shifts were attributed to damage to the sample microstructure (e.g. gel network disruption), which would lead to viscous-type behaviors such as permanent deformation and flow. Unlike the small deformation results, the LAOS behavior of the concentrated emulsions was not dependent on fish gelatin concentration. Systems with different microstructures showed similar nonlinear viscoelastic behaviors. The results of this study provided valuable information that can be used to incorporate concentrated emulsions in emulsion-based food formulations.

Keywords: concentrated emulsion, fish gelatin, microstructure, rheology

Procedia PDF Downloads 251

Authors: Siyamak Ziyaei, Siti Khalijah Mazlan, Petros Lappas

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Compressed Natural Gas (CNG) mainly consists of Methane CH₄ and has a low carbon to hydrogen ratio relative to other hydrocarbons. As a result, it has the potential to reduce CO₂ emissions by more than 20% relative to conventional fuels like diesel or gasoline Although Natural Gas (NG) has environmental advantages compared to other hydrocarbon fuels whether they are gaseous or liquid, its main component, CH₄, burns at a slower rate than conventional fuels A higher pressure and a leaner cylinder environment will overemphasize slow burn characteristic of CH₄. Lean combustion and high compression ratios are well-known methods for increasing the efficiency of internal combustion engines. In order to achieve successful CNG lean combustion in Spark Ignition (SI) engines, a strong ignition system is essential to avoid engine misfires, especially in ultra-lean conditions. Turbulent Jet Ignition (TJI) is an ignition system that employs a pre-combustion chamber to ignite the lean fuel mixture in the main combustion chamber using a fraction of the total fuel per cycle. TJI enables ultra-lean combustion by providing distributed ignition sites through orifices. The fast burn rate provided by TJI enables the ordinary SI engine to be comparable to other combustion systems such as Homogeneous Charge Compression Ignition (HCCI) or Controlled Auto-Ignition (CAI) in terms of thermal efficiency, through the increased levels of dilution without the need of sophisticated control systems. Due to the physical geometry of TJIs, which contain small orifices that connect the prechamber to the main chamber, scavenging is one of the main factors that reduce TJI performance. Specifically, providing the right mixture of fuel and air has been identified as a key challenge. The reason for this is the insufficient amount of air that is pushed into the pre-chamber during each compression stroke. There is also the problem that combustion residual gases such as CO₂, CO and NOx from the previous combustion cycle dilute the pre- chamber fuel-air mixture preventing rapid combustion in the pre-chamber. An air-controlled active TJI is presented in this paper in order to address these issues. By applying air to the pre-chamber at a sufficient pressure, residual gases are exhausted, and the air-fuel ratio is controlled within the pre-chamber, thereby improving the quality of combustion. This paper investigates the 3D-simulated combustion characteristics of a Direct Injected (DI-CNG) fuelled SI en- gine with a pre-chamber equipped with an air channel by using AVL FIRE software. Experiments and simulations were performed at the Worldwide Mapping Point (WWMP) at 1500 Revolutions Per Minute (RPM), 3.3 bar Indicated Mean Effective Pressure (IMEP), using only conventional spark plugs as the baseline. After validating simulation data, baseline engine conditions were set for all simulation scenarios at λ=1. Following that, the pre-chambers with and without an auxiliary fuel supply were simulated. In the simulated (DI-CNG) SI engine, active TJI was observed to perform better than passive TJI and spark plug. In conclusion, the active pre-chamber with an air channel demon-strated an improved thermal efficiency (ηth) over other counterparts and conventional spark ignition systems.

Keywords: turbulent jet ignition, active air control turbulent jet ignition, pre-chamber ignition system, active and passive pre-chamber, thermal efficiency, methane combustion, internal combustion engine combustion emissions

Procedia PDF Downloads 62

Authors: Ellana Boada, Eric Santos-Clotas, Alba Cabrera-Codony, Maria Martin, Lluis Baneras, Frederic Gich

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Volatile methylsiloxanes (VMS) are a group of manmade silicone compounds widely used in household and industrial applications that end up on the biogas produced through the anaerobic digestion of organic matter in landfills and wastewater treatment plants. The presence of VMS during the biogas energy conversion can cause damage on the engines, reducing the efficiency of this renewable energy source. Non regenerative adsorption onto activated carbon is the most widely used technology to remove siloxanes from biogas, while new trends point out that biotechnology offers a low-cost and environmentally friendly alternative to conventional technologies. The first objective of this research was to enrich, isolate and identify bacterial species able to grow using siloxane molecules as a sole carbon source: anoxic wastewater sludge was used as initial inoculum in liquid anoxic enrichments, adding D4 (as representative siloxane compound) previously adsorbed on activated carbon. After several months of acclimatization, liquid enrichments were plated onto solid media containing D4 and thirty-four bacterial isolates were obtained. 16S rRNA gene sequencing allowed the identification of strains belonging to the following species: Ciceribacter lividus, Alicycliphilus denitrificans, Pseudomonas aeruginosa and Pseudomonas citronellolis which are described to be capable to degrade toxic volatile organic compounds. Kinetic assays with 8 representative strains revealed higher cell growth in the presence of D4 compared to the control. Our second objective was to characterize the community composition and diversity of the microbial community present in the enrichments and to elucidate whether the isolated strains were representative members of the community or not. DNA samples were extracted, the 16S rRNA gene was amplified (515F & 806R primer pair), and the microbiome analyzed from sequences obtained with a MiSeq PE250 platform. Results showed that the retrieved isolates only represented a minor fraction of the microorganisms present in the enrichment samples, which were represented by Alpha, Beta, and Gamma proteobacteria as dominant groups in the category class thus suggesting that other microbial species and/or consortia may be important for D4 biodegradation. These results highlight the need of additional protocols for the isolation of relevant D4 degraders. Currently, we are developing molecular tools targeting key genes involved in siloxane biodegradation to identify and quantify the capacity of the isolates to metabolize D4 in batch cultures supplied with a synthetic gas stream of air containing 60 mg m⁻³ of D4 together with other volatile organic compounds found in the biogas mixture (i.e. toluene, hexane and limonene). The isolates were used as inoculum in a biotrickling filter containing lava rocks and activated carbon to assess their capacity for siloxane removal. Preliminary results of biotrickling filter performance showed 35% of siloxane biodegradation in a contact time of 14 minutes, denoting that biological siloxane removal is a promising technology for biogas upgrading.

Keywords: bacterial cultivation, biogas upgrading, microbiome, siloxanes

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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

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Authors: Jyh-Ping Chen, Yu-Tin Lai

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Wound healing is a complicated process involving overlapping hemostasis, inflammation, proliferation, and maturation phases. Ideal wound dressings can replace native skin functions in full thickness skin wounds through faster healing rate and also by reducing scar formation. Poly(lactic-co-glycolic acid) (PLGA) is an U.S. FDA approved biodegradable polymer to be used as ideal wound dressing material. Several in vitro and in vivo studies have demonstrated the effectiveness of curcumin in decreasing the release of inflammatory cytokines, inhibiting enzymes associated with inflammations, and scavenging free radicals that are the major cause of inflammation during wound healing. Heparin has binding affinities to various growth factors. With the unique and beneficial features offered by those molecules toward the complex process of wound healing, we postulate a composite wound dressing constructed from PLGA, curcumin and heparin would be a good candidate to accelerate scarless wound healing. In this work, we use electrospinning to prepare curcumin-loaded aligned PLGA nanofibrous membranes (PC NFMs). PC NFMs were further subject to oxygen plasma modification and surfaced-grafted with heparin through carbodiimide-mediated covalent bond formation to prepare curcumin-loaded PLGA-g-heparin (PCH) NFMs. The nanofibrous membranes could act as three-dimensional scaffolds to attract fibroblast migration, reduce inflammation, and increase wound-healing related growth factors concentrations at wound sites. From scanning electron microscopy analysis, the nanofibers in each NFM are with diameters ranging from 456 to 479 nm and with alignment angles within  0.5°. The NFMs show high tensile strength and good water absorptivity and provide suitable pore size for nutrients/wastes transport. Exposure of human dermal fibroblasts to the extraction medium of PC or PCH NFM showed significant protective effects against hydrogen peroxide than PLGA NFM. In vitro wound healing assays also showed that the extraction medium of PCH NFM showed significantly better migration ability toward fibroblasts than PC NFM, which is further better than PLGA NFM. The in vivo healing efficiency of the NFMs was further evaluated by a full thickness excisional wound healing diabetic rat model. After 14 days, PCH NFMs exhibits 86% wound closure rate, which is significantly different from other groups (79% for PC and 73% for PLGA NFM). Real-time PCR analysis indicated PC and PCH NFMs down regulated anti-oxidative enzymes like glutathione peroxidase (GPx) and superoxide dismutase (SOD), which are well-known transcription factors involved in cellular inflammatory responses to stimuli. From histology, the wound area treated with PCH NFMs showed more vascular lumen formation from immunohistochemistry of α-smooth muscle actin. The wound site also had more collagen type III (65.8%) expression and less collagen type I (3.5%) expression, indicating scar-less wound healing. From Western blot analysis, the PCH NFM showed good affinity toward growth factors from increased concentration of transforming growth factor-β (TGF-β) and fibroblast growth factor-2 (FGF-2) at the wound site to accelerate wound healing. From the results, we suggest PCH NFM as a promising candidate for wound dressing applications.

Keywords: Curcumin, heparin, nanofibrous membrane, poly(lactic-co-glycolic acid) (PLGA), wound dressing

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Authors: Dagmara Malina, Katarzyna Bialik-Wąs, Klaudia Pluta

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The growing significance of transdermal systems, in which skin is a route for systemic drug delivery, has generated a considerable amount of data which has resulted in a deeper understanding of the mechanisms of transport across the skin in the context of the controlled and prolonged release of active substances. One of such solutions may be the use of carrier systems based on intelligent polymers with different physicochemical properties. In these systems, active substances, e.g. drugs, can be conjugated (attached), immobilized, or encapsulated in a polymer matrix that is sensitive to specific environmental conditions (e.g. pH or temperature changes). Intelligent polymers can be divided according to their sensitivity to specific environmental stimuli such as temperature, pH, light, electric, magnetic, sound, or electromagnetic fields. Materials & methods—The first stage of the presented research concerned the synthesis of pH-sensitive polymeric carriers by a radical polymerization reaction. Then, the selected active substance (hydrocortisone) was introduced into polymeric carriers. In a further stage, bio-hybrid sodium alginate/poly(vinyl alcohol) – SA/PVA-based hydrogel matrices modified with various carrier-drug systems were prepared with the chemical cross-linking method. The conducted research included the assessment of physicochemical properties of obtained materials i.e. degree of hydrogel swelling and degradation studies as a function of pH in distilled water and phosphate-buffered saline (PBS) at 37°C in time. The gel fraction represents the insoluble gel fraction as a result of inter-molecule cross-linking formation was also measured. Additionally, the chemical structure of obtained hydrogels was confirmed using FT-IR spectroscopic technique. The dynamic light scattering (DLS) technique was used for the analysis of the average particle size of polymer-carriers and carrier-drug systems. The nanocarriers morphology was observed using SEM microscopy. Results & Discussion—The analysis of the encapsulated polymeric carriers showed that it was possible to obtain the time-stable empty pH-sensitive carrier with an average size 479 nm and the encapsulated system containing hydrocortisone with an average 543 nm, which was introduced into hydrogel structure. Bio-hybrid hydrogel matrices are stable materials, and the presence of an additional component: pH-sensitive carrier – hydrocortisone system, does not reduce the degree of cross-linking of the matrix nor its swelling ability. Moreover, the results of swelling tests indicate that systems containing higher concentrations of the drug have a slightly higher sorption capacity in each of the media used. All analyzed materials show stable and statically changing swelling values in simulated body fluids - there is no sudden fluid uptake and no rapid release from the material. The analysis of FT-IR spectra confirms the chemical structure of the obtained bio-hybrid hydrogel matrices. In the case of modifications with a pH-sensitive carrier, a much more intense band can be observed in the 3200-3500 cm⁻¹ range, which most likely originates from the strong hydrogen interactions that occur between individual components.

Keywords: hydrogels, polymer nanocarriers, sodium alginate/poly(vinyl alcohol) matrices, wound dressings.

Procedia PDF Downloads 120

Authors: Hasmik V. Zanginyan, Gayane S. Ghazaryan, Laura M. Hovsepyan

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Experimental autoimmune encephalomyelitis (EAE) is an inflammatory demyelinating disease of the central nervous system that is induced in laboratory animals by developing an immune response against myelin epitopes. The typical clinical course is ascending palsy, which correlates with inflammation and tissue damage in the thoracolumbar spinal cord, although the optic nerves and brain (especially the subpial white matter and brainstem) are also often affected. With multiple sclerosis, there is a violation of lipid metabolism in myelin. When membrane lipids (glycosphingolipids, phospholipids) are disturbed, metabolites not only play a structural role in membranes but are also sources of secondary mediators that transmit multiple cellular signals. The purpose of this study was to investigate the effect of ganglioside as a therapeutic agent in experimental multiple sclerosis. The biological activity of a ganglioside-containing medicinal preparation (Cronassial) was evaluated in an experimental model of multiple sclerosis in laboratory animals. An experimental model of multiple sclerosis in rats was obtained by immunization with myelin basic protein (MBP), as well as homogenization of the spinal cord or brain. EAE was induced by administering a mixture of an encephalitogenic mixture (EGM) with Complete Freund’s Adjuvant. Mitochondrial fraction was isolated in a medium containing 0,25 M saccharose and 0, 01 M tris buffer, pH - 7,4, by a method of differential centrifugation on a K-24 centrifuge. Glutathione peroxidase activity was assessed by reduction reactions of hydrogen peroxide (H₂O₂) and lipid hydroperoxides (ROOH) in the presence of GSH. LPO activity was assessed by the amount of malondialdehyde (MDA) in the total homogenate and mitochondrial fraction of the spinal cord and brain of control and experimental autoimmune encephalomyelitis rats. MDA was assessed by a reaction with Thiobarbituric acid. For statistical data analysis on PNP, SPSS (Statistical Package for Social Science) package was used. The nature of the distribution of the obtained data was determined by the Kolmogorov-Smirnov criterion. The comparative analysis was performed using a nonparametric Mann-Whitney test. The differences were statistically significant when р ≤ 0,05 or р ≤ 0,01. Correlational analysis was conducted using a nonparametric Spearman test. In the work, refrigeratory centrifuge, spectrophotometer LKB Biochrom ULTROSPECII (Sweden), pH-meter PL-600 mrc (Israel), guanosine, and ATP (Sigma). The study of the process of lipid peroxidation in the total homogenate of the brain and spinal cord in experimental animals revealed an increase in the content of malonic dialdehyde. When applied, Cronassial observed normalization of lipid peroxidation processes. Reactive oxygen species, causing lipid peroxidation processes, can be toxic both for neurons and for oligodendrocytes that form myelin, causing a violation of their lipid composition. The high content of lipids in the brain and the uniqueness of their structure determines the nature of the development of LPO processes. The lipid layer of cellular and intracellular membranes performs two main functions -barrier and matrix (structural). Damage to the barrier leads to dysregulation of intracellular processes and severe disorders of cellular functions.

Keywords: experimental autoimmune encephalomyelitis, multiple sclerosis, neuroinflammation, therapy

Procedia PDF Downloads 63

Authors: Kashima Arora, Monika Tomar, Vinay Gupta

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Biosensors have found potential applications ranging from environmental testing and biowarfare agent detection to clinical testing, health care, and cell analysis. This is driven in part by the desire to decrease the cost of health care and to obtain precise information more quickly about the health status of patient by the development of various biosensors, which has become increasingly prevalent in clinical testing and point of care testing for a wide range of biological elements. Uric acid is an important byproduct in human body and a number of pathological disorders are related to its high concentration in human body. In past few years, rapid growth in the development of new materials and improvements in sensing techniques have led to the evolution of advanced biosensors. In this context, metal oxide thin film based matrices due to their bio compatible nature, strong adsorption ability, high isoelectric point (IEP) and abundance in nature have become the materials of choice for recent technological advances in biotechnology. In the past few years, wide band-gap metal oxide semiconductors including ZnO, SnO₂ and CeO₂ have gained much attention as a matrix for immobilization of various biomolecules. Tin oxide (SnO₂), wide band gap semiconductor (Eg =3.87 eV), despite having multifunctional properties for broad range of applications including transparent electronics, gas sensors, acoustic devices, UV photodetectors, etc., it has not been explored much for biosensing purpose. To realize a high performance miniaturized biomolecular electronic device, rf sputtering technique is considered to be the most promising for the reproducible growth of good quality thin films, controlled surface morphology and desired film crystallization with improved electron transfer property. Recently, iron oxide and its composites have been widely used as matrix for biosensing application which exploits the electron communication feature of Fe, for the detection of various analytes using urea, hemoglobin, glucose, phenol, L-lactate, H₂O₂, etc. However, to the authors’ knowledge, no work is being reported on modifying the electronic properties of SnO₂ by implanting with suitable metal (Fe) to induce the redox couple in it and utilizing it for reagentless detection of uric acid. In present study, Fe implanted SnO₂ based matrix has been utilized for reagentless uric acid biosensor. Implantation of Fe into SnO₂ matrix is confirmed by energy-dispersive X-Ray spectroscopy (EDX) analysis. Electrochemical techniques have been used to study the response characteristics of Fe modified SnO₂ matrix before and after uricase immobilization. The developed uric acid biosensor exhibits a high sensitivity to about 0.21 mA/mM and a linear variation in current response over concentration range from 0.05 to 1.0 mM of uric acid besides high shelf life (~20 weeks). The Michaelis-Menten kinetic parameter (Km) is found to be relatively very low (0.23 mM), which indicates high affinity of the fabricated bioelectrode towards uric acid (analyte). Also, the presence of other interferents present in human serum has negligible effect on the performance of biosensor. Hence, obtained results highlight the importance of implanted Fe:SnO₂ thin film as an attractive matrix for realization of reagentless biosensors towards uric acid.

Keywords: Fe implanted tin oxide, reagentless uric acid biosensor, rf sputtering, thin film

Procedia PDF Downloads 148

Authors: K. Karapetyan, F. Tkhruni, A. Aghajanyan, T. S. Balabekyan, L. Arstamyan

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Introduction: Globalization of the food supply has created the conditions favorable for the emergence and spread of food-borne and especially dangerous pathogens (EDP) in developing countries. The fresh-cut fruit and vegetable industry is searching for alternatives to replace chemical treatments with biopreservative approaches that ensure the safety of the processed foods product. Antimicrobial compounds of lactic acid bacteria (LAB) possess bactericidal or bacteriostatic activity against intestinal pathogens, spoilage organisms and food-borne pathogens such as Listeria monocytogenes, Staphylococcus aureus and Salmonella. Endemic strains of LAB were isolated. The strains, showing broad spectrum of antimicrobial activity against food spoiling microorganisms, were selected. The genotyping by 16S rRNA sequencing, GS-PCR, RAPD PCR methods showed that they were presented by Lactobacillus rhamnosus109, L.plantarum 65, L.plantarum 66 and Enterococcus faecium 64 species. LAB are deposited in "Microbial Depository Center" (MDC) SPC "Armbiotechnology". Methods: LAB strains were isolated from different dairy products from rural households from the highland regions of Armenia. Serially diluted samples were spread on MRS (Merck, Germany) and hydrolyzed milk agar (1,2 % w/v). Single colonies from each LAB were individually inoculated in liquid MRS medium and incubated at 37oC for 24 hours. Culture broth with biomass was centrifuged at 10,000 g during 20 min for obtaining of cell free culture broth (CFC). The antimicrobial substances from CFC broth were purified by the combination of adsorption-desorption and ion-exchange chromatography methods. Separation of bacteriocins was performed using a HPLC method on "Avex ODS" C18 column. Mass analysis of peptides recorded on the device API 4000 in the electron ionization mode. The spot-on-lawn method on the test culture plated in the solid medium was applied. The antimicrobial activity is expressed in arbitrary units (AU/ml). Results. Purification of CFC broth of LAB allowed to obtain partially purified antimicrobial preparations which contains bacteriocins with broad spectrum of antimicrobial activity. Investigation of their main biochemical properties shown, that inhibitory activity of preparations is partially reduced after treatment with proteinase K, trypsin, pepsin, suggesting a proteinaceous nature of bacteriocin-like substances containing in CFC broth. Preparations preserved their activity after heat treatment (50-121 oC, 20 min) and were stable in the pH range 3–8. The results of SDS PAAG electrophoresis show that L.plantarum 66 and Ent.faecium 64 strains have one bacteriocin (BCN) with maximal antimicrobial activity with approximate molecular weight 2.0-3.0 kDa. From L.rhamnosus 109 two BCNs were obtained. Mass spectral analysis indicates that these bacteriocins have peptide bonds and molecular weight of BCN 1 and BCN 2 are approximately 1.5 kDa and 700 Da. Discussion: Thus, our experimental data shown, that isolated endemic strains of LAB are able to produce bacteriocins with high and different inhibitory activity against broad spectrum of microorganisms of different taxonomic group, such as Salmonella sp., Esherichia coli, Bacillus sp., L.monocytogenes, Proteus mirabilis, Staph. aureus, Ps. aeruginosa. Obtained results proved the perspectives for use of endemic strains in the preservation of foodstuffs. Acknowledgments: This work was realized with financial support of the Project Global Initiatives for Preliferation Prevention (GIPP) T2- 298, ISTC A-1866.

Keywords: antimicrobial activity, bacteriocins, endemic strains, food safety

Procedia PDF Downloads 541

Authors: Thembelihle Portia Lubisi, Malusi Ntandoyenkosi Mkhize, Jonas Kalebe Johakimu

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Fertilizers play an important role in maintaining the productivity and quality of plants. Inorganic fertilizers (containing nitrogen, phosphorus, and potassium) are largely used in South Africa as they are considered inexpensive and highly productive. When applied, a portion of the excess fertilizer will be retained in the soil, a portion enters water streams due to surface runoff or the irrigation system adopted. Excess nutrient from the fertilizers entering the water stream eventually results harmful algal blooms (HABs) in freshwater systems, which not only disrupt wildlife but can also produce toxins harmful to humans. Use of agro-chemicals such as pesticides and herbicides has been associated with increased antimicrobial resistance (AMR) in humans as the plants are consumed by humans. This resistance of bacterial poses a threat as it prevents the Health sector from being able to treat infectious disease. Archaeological studies have found that pyrolysis liquids were already used in the time of the Neanderthal as a biocide and plant protection product. Pyrolysis is thermal degradation process of plant biomass or organic material under anaerobic conditions leading to production of char, bio-oils and syn gases. Bio-oil constituents can be categorized as water soluble (wood vinegar) and water insoluble fractions (tar and light oils). Wood vinegar (pyro-ligneous acid) is said to contain contains highly oxygenated compounds including acids, alcohols, aldehydes, ketones, phenols, esters, furans, and other multifunctional compounds with various molecular weights and compositions depending on the biomass material derived from and pyrolysis operating conditions. Various researchers have found the wood vinegar to be efficient in the eradication of termites, effective in plant protection and plant growth, has antibacterial characteristics and was found effective in inhibiting the micro-organisms such as candida yeast, E-coli, etc. This study investigated characterisation of South African forestry product processing waste with intention of evaluating the potential of using the respective biomass waste as feedstock for boil oil production via pyrolysis process. Ability to use biomass waste materials in production of wood-vinegar has advantages that it does not only allows for reduction of environmental pollution and landfill requirement, but it also does not negatively affect food security. The biomass wastes investigated were from the popular tree types in KZN, which are, pine saw dust (PSD), pine bark (PB), eucalyptus saw dust (ESD) and eucalyptus bark (EB). Furthermore, the research investigates the possibility of mixing the different wastes with an aim to lessen the cost of raw material separation prior to feeding into pyrolysis process and mixing also increases the amount of biomass material available for beneficiation. A 50/50 mixture of PSD and ESD (EPSD) and mixture containing pine saw dust; eucalyptus saw dust, pine bark and eucalyptus bark (EPSDB). Characterisation of the biomass waste will look at analysis such as proximate (volatiles, ash, fixed carbon), ultimate (carbon, hydrogen, nitrogen, oxygen, sulphur), high heating value, structural (cellulose, hemicellulose and lignin) and thermogravimetric analysis.

Keywords: characterisation, biomass waste, saw dust, wood waste

Procedia PDF Downloads 36

Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

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Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

Procedia PDF Downloads 190

Authors: D. Malouch, M. Berchel, C. Dreanno, S. Stachowski-Haberkorn, P-A. Jaffres

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Biofilm is a predominant lifestyle chosen by bacteria. Whether it is developed on an immerged surface or a mobile biofilm known as flocs, the bacteria within this form of life show properties different from its planktonic ones. Within the biofilm, the self-formed matrix of Extracellular Polymeric Substances (EPS) offers hydration, resources capture, enhanced resistance to antimicrobial agents, and allows cell-communication. Biofouling is a complex natural phenomenon that involves biological, physical and chemical properties related to the environment, the submerged surface and the living organisms involved. Bio-colonization of artificial structures can cause various economic and environmental impacts. The increase in costs associated with the over-consumption of fuel from biocolonized vessels has been widely studied. Measurement drifts from submerged sensors, as well as obstructions in heat exchangers, and deterioration of offshore structures are major difficulties that industries are dealing with. Therefore, surfaces that inhibit biocolonization are required in different areas (water treatment, marine paints, etc.) and many efforts have been devoted to produce efficient and eco-compatible antifouling agents. The different steps of surface fouling are widely described in literature. Studying the biofilm and its stages provides a better understanding of how to elaborate more efficient antifouling strategies. Several approaches are currently applied, such as the use of biocide anti-fouling paint6 (mainly with copper derivatives) and super-hydrophobic coatings. While these two processes are proving to be the most effective, they are not entirely satisfactory, especially in a context of a changing legislation. Nowadays, the challenge is to prevent biofouling with non-biocide compounds, offering a cost effective solution, but with no toxic effects on marine organisms. Since the micro-fouling phase plays an important role in the regulation of the following steps of biofilm formation7, it is desired to reduce or delate biofouling of a given surface by inhibiting the micro fouling at its early stages. In our recent works, we reported that some amphiphilic compounds exhibited bacteriostatic or bactericidal properties at a concentration that did not affect eukaryotic cells. These remarkable properties invited us to assess this type of bio-inspired phospholipids9 to prevent the colonization of surfaces by marine bacteria. Of note, other studies reported that amphiphilic compounds interacted with bacteria leading to a reduction of their development. An amphiphilic compound is a molecule consisting of a hydrophobic domain and a polar head (ionic or non-ionic). These compounds appear to have interesting antifouling properties: some ionic compounds have shown antimicrobial activity, and zwitterions can reduce nonspecific adsorption of proteins. Herein, we investigate the potential of amphiphilic compounds as inhibitors of bacterial growth and marine biofilm formation. The aim of this study is to compare the efficacy of four synthetic phospholipids that features a cationic charge (BSV36, KLN47) or a zwitterionic polar-head group (SL386, MB2871) to prevent microfouling with marine bacteria. We also study the toxicity of these compounds in order to identify the most promising compound that must feature high anti-adhesive properties and a low cytotoxicity on two links representative of coastal marine food webs: phytoplankton and oyster larvae.

Keywords: amphiphilic phospholipids, bacterial biofilm, marine microfouling, non-toxic antifouling

Procedia PDF Downloads 110

Authors: Dmitriy Berillo, Areej K. A. Al-Jwaid, Jonathan L. Caplin, Andrew Cundy, Irina Savina

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Chlorophenols (CPs) are used as a precursor in the production of higher CPs and dyestuffs, and as a preservative. Contamination by CPs of the ground water is located in the range from 0.15-100mg/L. The EU has set maximum concentration limits for pesticides and their degradation products of 0.1μg/L and 0.5μg/L, respectively. People working in industries which produce textiles, leather products, domestic preservatives, and petrochemicals are most heavily exposed to CPs. The International Agency for Research on Cancers categorized CPs as potential human carcinogens. Existing multistep water purification processes for CPs such as hydrogenation, ion exchange, liquid-liquid extraction, adsorption by activated carbon, forward and inverse osmosis, electrolysis, sonochemistry, UV irradiation, and chemical oxidation are not always cost effective and can cause the formation of even more toxic or mutagenic derivatives. Bioremediation of CPs derivatives utilizing microorganisms results in 60 to 100% decontamination efficiency and the process is more environmentally-friendly compared with existing physico-chemical methods. Microorganisms immobilized onto a substrate show many advantages over free bacteria systems, such as higher biomass density, higher metabolic activity, and resistance to toxic chemicals. They also enable continuous operation, avoiding the requirement for biomass-liquid separation. The immobilized bacteria can be reused several times, which opens the opportunity for developing cost-effective processes for wastewater treatment. In this study, we develop a bioremediation system for CPs based on macroporous materials, which can be efficiently used for wastewater treatment. Conditions for the preparation of the macroporous material from specific bacterial strains (Pseudomonas mendocina and Rhodococus koreensis) were optimized. The concentration of bacterial cells was kept constant; the difference was only the type of cross-linking agents used e.g. glutaraldehyde, novel polymers, which were utilized at concentrations of 0.5 to 1.5%. SEM images and rheology analysis of the material indicated a monolithic macroporous structure. Phenol was chosen as a model system to optimize the function of the cryogel material and to estimate its enzymatic activity, since it is relatively less toxic and harmful compared to CPs. Several types of macroporous systems comprising live bacteria were prepared. The viability of the cross-linked bacteria was checked using Live/Dead BacLight kit and Laser Scanning Confocal Microscopy, which revealed the presence of viable bacteria with the novel cross-linkers, whereas the control material cross-linked with glutaraldehyde(GA), contained mostly dead cells. The bioreactors based on bacteria were used for phenol degradation in batch mode at an initial concentration of 50mg/L, pH 7.5 and a temperature of 30°C. Bacterial strains cross-linked with GA showed insignificant ability to degrade phenol and for one week only, but a combination of cross-linking agents illustrated higher stability, viability and the possibility to be reused for at least five weeks. Furthermore, conditions for CPs degradation will be optimized, and the chlorophenol degradation rates will be compared to those for phenol. This is a cutting-edge bioremediation approach, which allows the purification of waste water from sustainable compounds without a separation step to remove free planktonic bacteria. Acknowledgments: Dr. Berillo D. A. is very grateful to Individual Fellowship Marie Curie Program for funding of the research.

Keywords: bioremediation, cross-linking agents, cross-linked microbial cell, chlorophenol degradation

Procedia PDF Downloads 190

Authors: Łukasz Mazur, Kamil Domaradzki, Bartosz Kamecki, Justyna Ignaczak, Sebastian Molin, Aleksander Gil, Tomasz Brylewski

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The rising global power consumption necessitates the development of new energy storage solutions. Prospective technologies include solid oxide electrolyzer cells (SOECs), which convert surplus electrical energy into hydrogen. An electrolyzer cell consists of a porous anode, and cathode, and a dense electrolyte. Power output is increased by connecting cells into stacks using interconnects. Interconnects are currently made from high-chromium ferritic steels – for example, Crofer 22 APU – which exhibit high oxidation resistance and a thermal expansion coefficient that is similar to that of electrode materials. These materials have one disadvantage – their area-specific resistance (ASR) gradually increases due to the formation of a Cr₂O₃ scale on their surface as a result of oxidation. The chromia in the scale also reacts with the water vapor present in the reaction media, forming volatile chromium oxyhydroxides, which in turn react with electrode materials and cause their deterioration. The electrochemical efficiency of SOECs thus decreases. To mitigate this, the interconnect surface can be modified with protective-conducting coatings of spinel or other materials. The high prices of SOEC components -especially the Crofer 22 APU- have prevented their widespread adoption. More inexpensive counterparts, therefore, need to be found, and their properties need to be enhanced to make them viable. Candidates include the Nirosta 4016/1,4016 low-chromium ferritic steel with a chromium content of just 16.3 wt%. This steel's resistance to high-temperature oxidation was improved by depositing Gd₂O₃ nanoparticles on its surface via either dip coating or electrolysis. Modification with CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles deposited by means of spray pyrolysis was also tested. These methods were selected because of their low cost and simplicity of application. The aim of this study was to investigate the oxidation kinetics of Nirosta 4016/1,4016 modified using the afore-mentioned methods and to subsequently measure the obtained samples' ASR. The samples were oxidized for 100 h in the air as well as air/H₂O and Ar/H₂/H₂O mixtures at 1073 K. Such conditions reflect those found in the anode and cathode operating space during real-life use of SOECs. Phase and chemical composition and the microstructure of oxidation products were determined using XRD and SEM-EDS. ASR was measured over the range of 623-1073 K using a four-point, two-probe DC technique. The results indicate that the applied nanoparticles improve the oxidation resistance and electrical properties of the studied layered systems. The properties of individual systems varied significantly depending on the applied reaction medium. Gd₂O₃ nanoparticles improved oxidation resistance to a greater degree than either CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles. On the other hand, the cerium-containing nanoparticles improved electrical properties regardless of the reaction medium. The ASR values of all surface-modified steel samples were below the 0.1 Ω.cm² threshold set for interconnect materials, which was exceeded in the case of the unmodified reference sample. It can be concluded that the applied modifications increased the oxidation resistance of Nirosta 4016/1.4016 to a level that allows its use as SOEC interconnect material. Acknowledgments: Funding of Research project supported by program "Excellence initiative – research university" for the AGH University of Krakow" is gratefully acknowledged (TB).

Keywords: cerium oxide, ferritic stainless steel, gadolinium oxide, interconnect, SOEC

Procedia PDF Downloads 46

Authors: Xu Fei (Philip) WU

Abstract:

As waste recycling concept been accepted more and more in modern societies, the organic portion of the municipal waste become a sires issue in today’s life. Depend on location and season, the organic waste can bee anywhere between 40-65% of total municipal solid waste. Also composting and anaerobic digestion technologies been applied in this field for years, however both process have difficulties been selected by economical and environmental factors. Beside environmental pollution and risk of virus spread, the compost is not a product been welcomed by people even the waste management has to give up them at no cost. The anaerobic digester has to have 70% of water and keep at 35 degree C or above; base on above conditions, the retention time only can be up to two weeks and remain solid has to be dewater and composting again. The enhancive waste water treatment has to be added after. Because these reasons, the voice of suggesting cancelling recycling program and turning all waste to mass burn incinerations have been raised-A process has already been proved has least energy efficiency and most air pollution problem associated process. A newly developed WXF Bio-energy process employs recently developed and patented pre-designed separation, multi-layer and multi-cavity successive bioreactor landfill technology. It features an improved leachate recycling technology, technologies to maximize the biogas generation rate and a reduced overall turnaround period on the land. A single properly designed and operated site can be used indefinitely. In this process, all collected biogas will be processed to eliminate H2S and other hazardous gases. The methane, carbon dioxide and hydrogen will be utilized in a proprietary process to manufacture methanol which can be sold to mitigate operating costs of the landfill. This integration of new processes offers a more advanced alternative to current sanitary landfill, incineration and compost technology. Xu Fei (Philip) Wu Xu Fei Wu is founder and Chief Scientist of W&Y Environmental International Inc. (W & Y), a Canadian environmental and sustainable energy technology company with patented landfill processes and proprietary waste to energy technologies. He has worked in environmental and sustainable energy fields over the last 25 years. Before W&Y, he worked for Conestoga-Rovers & Associates Limited, Microbe Environmental Science and Technology Inc. of Canada and The Ministry of Nuclear Industry and Ministry of Space Flight Industry of China. Xu Fei Wu holds a Master of Engineering Science degree from The University of Western Ontario. I wish present this paper as an oral presentation only Selected Conference Presentations: • “Removal of Phenolic Compounds with Algae” Presented at 25th Canadian Symposium on Water Pollution Research (CAWPRC Conference), Burlington, Ontario Canada. February, 1990 • “Removal of Phenolic Compounds with Algae” Presented at Annual Conference of Pollution Control Association of Ontario, London, Ontario, Canada. April, 1990 • “Removal of Organochlorine Compounds in a Flocculated Algae Photo-Bioreactor” Presented at International Symposium on Low Cost and Energy Saving Wastewater Treatment Technologies (IAWPRC Conference), Kiyoto, Japan, August, 1990 • “Maximizing Production and Utilization of Landfill Gas” 2009 Wuhan International Conference on Environment(CAWPRC Conference, sponsored by US EPA) Wuhan, China. October, 2009. • “WXF Bio-Energy-A Green, Sustainable Waste to Energy Process” Presented at 9Th International Conference Cooperation for Waste Issues, Kharkiv, Ukraine March, 2012 • “A Lannfill Site Can Be Recycled Indefinitely” Presented at 28th International Conference on solid Waste Technology and Management, Philadelphia, Pennsylvania, USA. March, 2013. Hosted by The Journal of Solid Waste Technology and Management.

Keywords: green fuel, waste management, bio-energy, sustainable development, methanol

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Authors: M. Agostini, A. Sonato, G. Greco, M. Travagliati, G. Ruffato, E. Gazzola, D. Liuni, F. Romanato, M. Cecchini

Abstract:

Since their first demonstration in the early 1980s, surface plasmon resonance (SPR) sensors have been widely recognized as useful tools for detecting chemical and biological species, and the interest of the scientific community toward this technology has known a rapid growth in the past two decades owing to their high sensitivity, label-free operation and possibility of real-time detection. Recent works have suggested that a turning point in SPR sensor research would be the combination of SPR strategies with other technologies in order to reduce human handling of samples, improve integration and plasmonic sensitivity. In this light, microfluidics has been attracting growing interest. By properly designing microfluidic biochips it is possible to miniaturize the analyte-sensitive areas with an overall reduction of the chip dimension, reduce the liquid reagents and sample volume, improve automation, and increase the number of experiments in a single biochip by multiplexing approaches. However, as the fluidic channel dimensions approach the micron scale, laminar flows become dominant owing to the low Reynolds numbers that typically characterize microfluidics. In these environments mixing times are usually dominated by diffusion, which can be prohibitively long and lead to long-lasting biochemistry experiments. An elegant method to overcome these issues is to actively perturb the liquid laminar flow by exploiting surface acoustic waves (SAWs). With this work, we demonstrate a new approach for SPR biosensing based on the combination of microfluidics, SAW-induced mixing and the real-time phase-interrogation grating-coupling SPR technology. On a single lithium niobate (LN) substrate the nanostructured SPR sensing areas, interdigital transducer (IDT) for SAW generation and polydimethylsiloxane (PDMS) microfluidic chambers were fabricated. SAWs, impinging on the microfluidic chamber, generate acoustic streaming inside the fluid, leading to chaotic advection and thus improved fluid mixing, whilst analytes binding detection is made via SPR method based on SPP excitation via gold metallic grating upon azimuthal orientation and phase interrogation. Our device has been fully characterized in order to separate for the very first time the unwanted SAW heating effect with respect to the fluid stirring inside the microchamber that affect the molecules binding dynamics. Avidin/biotin assay and thiol-polyethylene glycol (bPEG-SH) were exploited as model biological interaction and non-fouling layer respectively. Biosensing kinetics time reduction with SAW-enhanced mixing resulted in a ≈ 82% improvement for bPEG-SH adsorption onto gold and ≈ 24% for avidin/biotin binding—≈ 50% and 18% respectively compared to the heating only condition. These results demonstrate that our biochip can significantly reduce the duration of bioreactions that usually require long times (e.g., PEG-based sensing layer, low concentration analyte detection). The sensing architecture here proposed represents a new promising technology satisfying the major biosensing requirements: scalability and high throughput capabilities. The detection system size and biochip dimension could be further reduced and integrated; in addition, the possibility of reducing biological experiment duration via SAW-driven active mixing and developing multiplexing platforms for parallel real-time sensing could be easily combined. In general, the technology reported in this study can be straightforwardly adapted to a great number of biological system and sensing geometry.

Keywords: biosensor, microfluidics, surface acoustic wave, surface plasmon resonance

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Authors: Katerina Zaharieva, Katya Milenova, Zara Cherkezova-Zheleva, Alexander Eliyas, Boris Kunev, Ivan Mitov

Abstract:

The synthesized nanosized manganese ferrite-type of samples have been tested as photocatalysts in the reaction of oxidative degradation of model contaminant Reactive Black 5 (RB5) dye in aqueous solutions under UV irradiation. As it is known this azo dye is applied in the textile-coloring industry and it is discharged into the waterways causing pollution. The co-precipitation procedure has been used for the synthesis of manganese ferrite-type of materials: Sample 1 - Mn0.25Fe2.75O4, Sample 2 - Mn0.5Fe2.5O4 and Sample 3 - MnFe2O4 from 0.03M aqueous solutions of MnCl2•4H2O, FeCl2•4H2O and/or FeCl3•6H2O and 0.3M NaOH in appropriate amounts. The mechanochemical activation of co-precipitated ferrite-type of samples has been performed in argon (Samples 1 and 2) or in air atmosphere (Sample 3) for 2 hours at a milling speed of 500 rpm. The mechano-chemical treatment has been carried out in a high energy planetary ball mill type PM 100, Retsch, Germany. The mass ratio between balls and powder was 30:1. As a result mechanochemically activated Sample 4 - Mn0.25Fe2.75O4, Sample 5 - Mn0.5Fe2.5O4 and Sample 6 - MnFe2O4 have been obtained. The synthesized manganese ferrite-type photocatalysts have been characterized by X-ray diffraction method and Moessbauer spectroscopy. The registered X-ray diffraction patterns and Moessbauer spectra of co-precipitated ferrite-type of materials show the presence of manganese ferrite and additional akaganeite phase. The presence of manganese ferrite and small amounts of iron phases is established in the mechanochemically treated samples. The calculated average crystallite size of manganese ferrites varies within the range 7 – 13 nm. This result is confirmed by Moessbauer study. The registered spectra show superparamagnetic behavior of the prepared materials at room temperature. The photocatalytic investigations have been made using polychromatic UV-A light lamp (Sylvania BLB, 18 W) illumination with wavelength maximum at 365 nm. The intensity of light irradiation upon the manganese ferrite-type photocatalysts was 0.66 mW.cm-2. The photocatalytic reaction of oxidative degradation of RB5 dye was carried out in a semi-batch slurry photocatalytic reactor with 0.15 g of ferrite-type powder, 150 ml of 20 ppm dye aqueous solution under magnetic stirring at rate 400 rpm and continuously feeding air flow. The samples achieved adsorption-desorption equilibrium in the dark period for 30 min and then the UV-light was turned on. After regular time intervals aliquot parts from the suspension were taken out and centrifuged to separate the powder from solution. The residual concentrations of dye were established by a UV-Vis absorbance single beam spectrophotometer CamSpec M501 (UK) measuring in the wavelength region from 190 to 800 nm. The photocatalytic measurements determined that the apparent pseudo-first-order rate constants calculated by linear slopes approximating to first order kinetic equation, increase in following order: Sample 3 (1.1х10-3 min-1) < Sample 1 (2.2х10-3 min-1) < Sample 2 (3.3 х10-3 min-1) < Sample 4 (3.8х10-3 min-1) < Sample 6 (11х10-3 min-1) < Sample 5 (15.2х10-3 min-1). The mechanochemically activated manganese ferrite-type of photocatalyst samples show significantly higher degree of oxidative degradation of RB5 dye after 120 minutes of UV light illumination in comparison with co-precipitated ferrite-type samples: Sample 5 (92%) > Sample 6 (91%) > Sample 4 (63%) > Sample 2 (53%) > Sample 1 (42%) > Sample 3 (15%). Summarizing the obtained results we conclude that the mechanochemical activation leads to a significant enhancement of the degree of oxidative degradation of the RB5 dye and photocatalytic activity of tested manganese ferrite-type of catalyst samples under our experimental conditions. The mechanochemically activated Mn0.5Fe2.5O4 ferrite-type of material displays the highest photocatalytic activity (15.2х10-3 min-1) and degree of oxidative degradation of the RB5 dye (92%) compared to the other synthesized samples. Especially a significant improvement in the degree of oxidative degradation of RB5 dye (91%) has been determined for mechanochemically treated MnFe2O4 ferrite-type of sample with the highest extent of substitution of iron ions by manganese ions than in the case of the co-precipitated MnFe2O4 sample (15%). The mechanochemically activated manganese ferrite-type of samples show good photocatalytic properties in the reaction of oxidative degradation of RB5 azo dye in aqueous solutions and it could find potential application for dye removal from wastewaters originating from textile industry.

Keywords: nanostructured manganese ferrite-type materials, photocatalytic activity, Reactive Black 5, water treatment

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Authors: Mina Naeini, Thomas A. Adams II

Abstract:

Solid Oxide Fuel Cells (SOFCs) feature high electrical efficiency and generate substantial amounts of waste heat that make them suitable for integrated community energy systems (ICEs). By harvesting and distributing the waste heat through hot water pipelines, SOFCs can meet thermal demand of the communities. Therefore, they can replace traditional gas boilers and reduce greenhouse gas (GHG) emissions. Despite these advantages of SOFCs over competing power generation units, this technology has not been successfully commercialized in large-scale to replace traditional generators in ICEs. One reason is that SOFC performance deteriorates over long-term operation, which makes it difficult to find the proper sizing of the cells for a particular ICE system. In order to find the optimal sizing and operating conditions of SOFCs in a community, a proper knowledge of degradation mechanisms and effects of operating conditions on SOFCs long-time performance is required. The simplified SOFC models that exist in the current literature usually do not provide realistic results since they usually underestimate rate of performance drop by making too many assumptions or generalizations. In addition, some of these models have been obtained from experimental data by curve-fitting methods. Although these models are valid for the range of operating conditions in which experiments were conducted, they cannot be generalized to other conditions and so have limited use for most ICEs. In the present study, a general, detailed degradation-based model is proposed that predicts the performance of conventional SOFCs over a long period of time at different operating conditions. Conventional SOFCs are composed of Yttria Stabilized Zirconia (YSZ) as electrolyte, Ni-cermet anodes, and LaSr₁₋ₓMnₓO₃ (LSM) cathodes. The following degradation processes are considered in this model: oxidation and coarsening of nickel particles in the Ni-cermet anodes, changes in the pore radius in anode, electrolyte, and anode electrical conductivity degradation, and sulfur poisoning of the anode compartment. This model helps decision makers discover the optimal sizing and operation of the cells for a stable, efficient performance with the fewest assumptions. It is suitable for a wide variety of applications. Sulfur contamination of the anode compartment is an important cause of performance drop in cells supplied with hydrocarbon-based fuel sources. H₂S, which is often added to hydrocarbon fuels as an odorant, can diminish catalytic behavior of Ni-based anodes by lowering their electrochemical activity and hydrocarbon conversion properties. Therefore, the existing models in the literature for H₂-supplied SOFCs cannot be applied to hydrocarbon-fueled SOFCs as they only account for the electrochemical activity reduction. A regression model is developed in the current work for sulfur contamination of the SOFCs fed with hydrocarbon fuel sources. The model is developed as a function of current density and H₂S concentration in the fuel. To the best of authors' knowledge, it is the first model that accounts for impact of current density on sulfur poisoning of cells supplied with hydrocarbon-based fuels. Proposed model has wide validity over a range of parameters and is consistent across multiple studies by different independent groups. Simulations using the degradation-based model illustrated that SOFCs voltage drops significantly in the first 1500 hours of operation. After that, cells exhibit a slower degradation rate. The present analysis allowed us to discover the reason for various degradation rate values reported in literature for conventional SOFCs. In fact, the reason why literature reports very different degradation rates, is that literature is inconsistent in definition of how degradation rate is calculated. In the literature, the degradation rate has been calculated as the slope of voltage versus time plot with the unit of voltage drop percentage per 1000 hours operation. Due to the nonlinear profile of voltage over time, degradation rate magnitude depends on the magnitude of time steps selected to calculate the curve's slope. To avoid this issue, instantaneous rate of performance drop is used in the present work. According to a sensitivity analysis, the current density has the highest impact on degradation rate compared to other operating factors, while temperature and hydrogen partial pressure affect SOFCs performance less. The findings demonstrated that a cell running at lower current density performs better in long-term in terms of total average energy delivered per year, even though initially it generates less power than if it had a higher current density. This is because of the dominant and devastating impact of large current densities on the long-term performance of SOFCs, as explained by the model.

Keywords: degradation rate, long-term performance, optimal operation, solid oxide fuel cells, SOFCs

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