37 resultados para ENGINEERING, CHEMICAL

em Deakin Research Online - Australia


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Precise and reliable modelling of polymerization reactor is challenging due to its complex reaction mechanism and non-linear nature. Researchers often make several assumptions when deriving theories and developing models for polymerization reactor. Therefore, traditional available models suffer from high prediction error. In contrast, data-driven modelling techniques provide a powerful framework to describe the dynamic behaviour of polymerization reactor. However, the traditional NN prediction performance is significantly dropped in the presence of polymerization process disturbances. Besides, uncertainty effects caused by disturbances present in reactor operation can be properly quantified through construction of prediction intervals (PIs) for model outputs. In this study, we propose and apply a PI-based neural network (PI-NN) model for the free radical polymerization system. This strategy avoids assumptions made in traditional modelling techniques for polymerization reactor system. Lower upper bound estimation (LUBE) method is used to develop PI-NN model for uncertainty quantification. To further improve the quality of model, a new method is proposed for aggregation of upper and lower bounds of PIs obtained from individual PI-NN models. Simulation results reveal that combined PI-NN performance is superior to those individual PI-NN models in terms of PI quality. Besides, constructed PIs are able to properly quantify effects of uncertainties in reactor operation, where these can be later used as part of the control process. © 2014 Taiwan Institute of Chemical Engineers.

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A membrane reactor allows for simultaneous separation and reaction, and thus, can play a good role to produce value-added chemicals. In this work, we demonstrated such a membrane reactor based on fluorite oxide samarium-doped ceria (SDC) using an external short-circuit concept for oxygen permeation. The fluorite phase was employed to impart its high structural stability, while its limited electronic conductivity was overcome by the application of an external short circuit to function the SDC membrane for oxygen transport. On one side of the membrane, i.e., feed side, carbon dioxide decomposition into carbon monoxide and oxygen was carried out with the aid of a Pt or Ag catalyst. The resultant oxygen was concurrently depleted on the membrane surface and transported to the other side of the membrane, favorably shifting this equilibrium-limited reaction to the product side. The transported oxygen on the permeate side with the aid of a GdNi/Al2O3 catalyst was then consumed by the reaction with methane to form syngas, i.e., carbon monoxide and hydrogen. As such, the required driving force for gas transport through the membrane can be sustained by coupling two different reactions in one membrane reactor, whose stability to withstand these different gases at high temperatures is attained in this paper. We also examined the effect of the membrane thickness, oxygen ionic transport rate, and CO2 and CH4 flow rates to the membrane reactor performance. More importantly, here, we proved the feasibility of a highly stable membrane reactor based on an external short circuit as evidenced by achieving the constant performance in CO selectivity, CH4 conversion, CO2 conversion, and O2 flux during 100 h of operation and unaltered membrane structure after this operation together with the coking resistance.

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Reliable, safe and high performance solid electrolytes are a critical step in the advancement of high energy density secondary batteries. In the present work we demonstrate a novel solid electrolyte based on the organic ionic plastic crystal (OIPC) triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI). With the addition of 4 mol% LiFSI, the OIPC shows a high conductivity of 0.26 mS cm-1 at 22 °C. The ion transport mechanisms have been rationalized by compiling thermal phase behaviour and crystal structure information obtained by variable temperature synchrotron X-ray diffraction. With a large electrochemical window (ca. 6 V) and importantly, the formation of a stable and highly conductive solid electrolyte interphase (SEI), we were able to cycle lithium cells (LiLiFePO4) at 30 °C and 20 °C at rates of up to 1 C with good capacity retention. At the 0.1 C rate, about 160 mA h g-1 discharge capacity was achieved at 20 °C, which is the highest for OIPC based cells to date. It is anticipated that these small phosphonium cation and [FSI] anion based OIPCs will show increasing significance in the field of solid electrolytes.

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In this paper, prediction interval (PI)-based modelling techniques are introduced and applied to capture the nonlinear dynamics of a polystyrene batch reactor system. Traditional NN models are developed using experimental datasets with and without disturbances. Simulation results indicate that traditional NNs cannot properly handle disturbances in reactor data and demonstrate a poor forecasting performance, with an average MAPE of 22% in the presence of disturbances. The lower upper bound estimation (LUBE) method is applied for the construction of PIs to quantify uncertainties associated with forecasts. The simulated annealing optimization technique is employed to adjust NN parameters for minimization of an innovative PI-based cost function. The simulation results reveal that the LUBE method generates quality PIs without requiring prohibitive computations. As both calibration and sharpness of PIs are practically and theoretically satisfactory, the constructed PIs can be used as part of the decision-making and control process of polymerization reactors. © 2014 The Institution of Chemical Engineers.

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A nanocomposite consisting of reduced graphene oxide and zinc oxide nanoparticles (RGO/ZnO) with unique structural features was developed as an efficient, sustainable, amphiphilic, heterogeneous catalyst for the synthesis of various 3-substituted indoles in water. The catalyst was recycled six times without significant loss in catalytic activity. The higher environmental compatibility and sustainability factors such as smaller E-factor and higher atom economy make the present methodology a true green and sustainable process for the synthesis of various biologically important 3-substituted indoles.

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In this paper, our goal is to examine the unit root null hypothesis in energy consumption for Australian states and territory. We consider sectoral energy consumption for Australia and its six states and one territory using time series data for the period 1973-2007. This is the first study that does this. Generally, except for some cases in South Australia, we find strong support that shocks to energy consumption have a temporary effect on energy consumption in Australia. © 2009 Elsevier Ltd. All rights reserved.

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The goal of this paper is to undertake a panel data investigation of long-run Granger causality between electricity consumption and real GDP for seven panels, which together consist of 93 countries. We use a new panel causality test and find that in the long-run both electricity consumption and real GDP have a bidirectional Granger causality relationship except for the Middle East where causality runs only from GDP to electricity consumption. Finally, for the G6 panel the estimates reveal a negative sign effect, implying that increasing electricity consumption in the six most industrialised nations will reduce GDP. © 2010 Elsevier Ltd. All rights reserved.

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Silk particles of different sizes and shapes were produced by milling and interactions with a series of polar and non-polar gaseous probes were investigated using an inverse gas chromatography technique. The surface energy of all silk materials is mostly determined by long range dispersive interactions such as van der Waals forces. The surface energy increases and surface energy heterogeneity widens after milling. All samples have amphoteric surfaces and the concentration of acidic groups increases after milling while the surfaces remain predominantly basic. We also examined powder compression and flow behaviours using a rheometer. Increase in surface energy, surface area, and static charges in sub-micron air jet milled particles contributed to their aggregation and therefore improved flowability. However they collapse under large pressures and form highly cohesive powder. Alkaline hydrolysis resulted in more crystalline fibres which on milling produced particles with higher density, lower surface energy and improved flowability. The compressibility, bulk density and cohesion of the powders depend on the surface energy as well as on particle size, surface area, aggregation state and the testing conditions, notably the consolidated and unconsolidated states. The study has helped in understanding how surface energy and flowability of particles can be changed via different fabrication approaches.

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The performances of three advanced non-linear controllers are analyzed for the optimal set point tracking of styrene free radical polymerization (FRP) in batch reactors. The three controllers are the artificial neural network-based MPC (NN-MPC), the artificial fuzzy logic controller (FLC) as well as the generic model controller (GMC). A recently developed hybrid model (Hosen et al., 2011a. Asia-Pac. J. Chem. Eng. 6(2), 274) is utilized in the control study to design and tune the proposed controllers. The optimal minimum temperature profiles are determined using the Hamiltonian maximum principle. Different types of disturbances are introduced and applied to examine the stability of controller performance. The experimental studies revealed that the performance of the NN-MPC is superior to that of FLC and GMC. © 2013 The Institution of Chemical Engineers.

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Biofilm formation on membranes during water desalination operation and pre-treatments limits performance and causes premature membrane degradation. Here, we apply a novel surface modification technique to incorporate anti-microbial metal particles into the outer layer of four types of commercial polymeric membranes by cold spray. The particles are anchored on the membrane surface by partial embedment within the polymer matrix. Although clear differences in particle surface loadings and response to the cold spray were shown by SEM, the hybrid micro-filtration and ultra-filtration membranes were found to exhibit excellent anti-bacterial properties. Poly(sulfone) ultra-filtration membranes were used as for cross-flow filtration of Escherichia coli bacteria solutions to investigate the impact of the cold spray on the material[U+05F3]s integrity. The membranes were characterized by SEM-EDS, FT-IR and TGA and challenged in filtration tests. No bacteria passed through the membrane and filtrate water quality was good, indicating the membranes remained intact. No intact bacteria were found on hybrid membranes, loaded with up to 15. wt% silver, indicating the treatment was lysing bacteria on contact. However, permeation of the hybrid membranes was found to be reduced compared to control non-modified poly(sulfone) membranes due to the presence of the particles across the membrane material. The implementation of cold spray technology for the modification of commercial membrane products could lead to significant operational savings in the field of desalination and water pre-treatments.

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Silk particles were produced by regenerating from silk solution, and using a milling method. In the regenerated silk particle production, two methods which are reported to render submicron silk particles were selected. Their particle sizes and structures were compared with particles of milling method already developed by us. The volume median average particle sizes (d(0.5)) of regenerated particles were much higher than what was reported previously. In contrast, milling method could produce particles with adjustable particle sizes ranging from micron to submicron level. All the milled particles had advantage of at least 15. °C higher thermal decomposition temperature than regenerated particles. They had silk II structure, and the crystallinity reduced as particle fineness increased, but remained higher than regenerated particles of similar sizes. © 2014 Elsevier B.V.

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Vacuum fluidised beds have a distinct advantage of being operated with reduced mass consumption of the fluidising media. However, a low quality of fluidisation reduces the opportunity to utilise the bubbling regime in vacuum fluidised beds. Fluidisation maps are often used to depict the interface between the quiescent, bubbling and slugging regimes inside a fluidised bed. Such maps have been obtained by visual observations of the fluidisation interface in transparent fluidised beds. For beds which are visually inaccessible fluidisation maps are difficult to obtain. The present work therefore attempts to model the interface travel in a vacuum fluidised bed. The pressure gradient due to the bed weight has been determined to be a main contributor for fluidisation/defluidisation under vacuum. A simple analytical model based on the pressure gradient (PG model) is developed to predict the interface location in a vacuum fluidised bed. For a segregated bed, the Gibilaro-Rowe (GR) model is modified and used to predict the jetsam layer growth along with the fluidisation interface. The predictions are compared with the experimental data for minimally and highly segregated particles and it is seen that for non-segregated powders the predictions are quite accurate. Lack of sufficient knowledge of bubble characteristics, however, impeded accurate prediction of the jetsam growth especially at high flow rates. However, an approximate complete fluidisation interface is successfully predicted using the GR-PG model. © 2014 Elsevier B.V.

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A simple in-situ synthesis route for gold nanoparticles (NPs) was developed to realize multifunctions for silk fabrics. The gold NPs were prepared in a heated solution containing white silk fabric samples. The silk fabrics were colored red and brown by the gold NPs because of their localized surface plasmon resonance (LSPR) property. Gold nanospheres on silk were obtained at a low gold content, and gold nanoplates were synthesized as the gold content increased. The silk fabrics treated with gold NPs showed good light fastness. Moreover, the gold NPs endowed silk fabrics with strong antibacterial activity, excellent UV protection property and enhanced thermal conductivity. © 2013 Elsevier Ltd. All rights reserved.

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This study examined the structure, thermal property, and ion adsorption of silk particles. The particles were prepared by attritor-bead mill combination, using alkaline (pH10) charge repulsion and surfactant steric repulsion methods. Both methods produced particles with a dominant β-sheet structure, similar to the silk fibre. There was no significant difference in the decomposition temperatures for either the silk fibre or the micro/nano silk particles. An important finding from this study is clear evidence of reduction of amorphous content during the final stage of powdering using the bead mill. As a result, despite reduction in β-sheet crystallites with the progressive milling, the relative β-sheet content actually increased during this process. However, intermolecular forces between the β-sheets reduced significantly and hence the XRD results showed significant reduction in crystallinity in nano silk particles but crystal forming segments remained with β-sheet conformations after milling. The structural change influenced the ion-adsorption property where particle-size reduction resulted in a significant increase in both the rate and volume of HCrO4- adsorption. © 2014 Elsevier B.V.

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Photoinduced shape conversion of silver nanoparticles was realized using sunlight. The silver seeds were transformed to silver nanoprisms under sunlight when the concentration of citrate was low (≤5.0×10-4M). Nevertheless, sunlight converted the obtained silver nanoprisms to silver nanodecahedrons when the concentration of citrate in reaction system was increased. It was found that the ultraviolet light from sunlight played a vital role in the shape conversion from nanoprism to nanodecahedron. Lighting power density did not influence the shape conversion except for reaction rate. Besides, the silver nanodecahedrons were synthesized in the mixed solution of AgNO3 and citrate in absence of silver seeds through irradiation by simulated sunlight. The mechanism on the sunlight induced synthesis of silver nanoparticles was discussed. Anisotropic silver nanoparticles including nanoprisms and nanodecahedrons were obtained through controlling the citrate concentration and irradiation time by sunlight from green light source.