Microwave-assisted enzymatic synthesis of beef tallow biodiesel

Optimal conditions for the microwave-assisted enzymatic synthesis of biodiesel have been developed by a full 2(2) factorial design leading to a set of seven runs with different combinations of molar ratio and temperature. The main goal was to reduce the reaction time preliminarily established by a process of conventional heating. Reactions yielding biodiesel, in which beef tallow and ethanol used as raw materials were catalyzed by lipase from Burkholderia cepacia immobilized on silica-PVA and microwave irradiations within the range of 8-15 W were performed to reach the reaction temperature. Under optimized conditions (1:6 molar ratio of beef tallow to ethanol molar ratio at 50A degrees C) almost total conversion of the fatty acid presented in the original beef tallow was converted into ethyl esters in a reaction that required 8 h, i.e., a productivity of about 92 mg ethyl esters g(-1) h(-1). This represents an increase of sixfold for the process carried out under conventional heating. In general, the process promises low energy demand and higher biodiesel productivity. The microwave assistance speeds up the enzyme catalyzed reactions, decreases the destructive effects on the enzyme of the operational conditions such as, higher temperature, stability, and specificity to its substrate, and allows the entire reaction medium to be heated uniformly.

Phenol biodegradation by a microbial consortium: application of artificial neural network (ANN) modelling

In this study, an effective microbial consortium for the biodegradation of phenol was grown under different operational conditions, and the effects of phosphate concentration (1.4 g L-1, 2.8 g L-1, 4.2 g L-1), temperature (25 degrees C, 30 degrees C, 35 degrees C), agitation (150 rpm, 200 rpm, 250 rpm) and pH (6, 7, 8) on phenol degradation were investigated, whereupon an artificial neural network (ANN) model was developed in order to predict degradation. The learning, recall and generalization characteristics of neural networks were studied using data from the phenol degradation system. The efficiency of the model generated by the ANN was then tested and compared with the experimental results obtained. In both cases, the results corroborate the idea that aeration and temperature are crucial to increasing the efficiency of biodegradation.

Performance tests of two small trigeneration pilot plants

Trigeneration systems have been used with advantage in the last years in distributed electricity generation systems as a function of a growth of natural gas pipeline network distribution system, tax incentives, and energy regulation policies. Typically, a trigeneration system is used to produce electrical power simultaneously with supplying heating and cooling load by recovering the combustion products thermal power content that otherwise would be driven to atmosphere. Concerning that, two small scale trigeneration plants have been tested for overall efficiency evaluation and operational comparison. The first system is based on a 30 kW (ISO) natural gas powered microturbine, and the second one uses a 26 kW natural gas powered internal combustion engine coupled to an electrical generator as a prime mover. The stack gases from both machines were directed to a 17.6 kW ammonia-water absorption refrigeration chiller for producing chilled water first and next to a water heat recovery boiler in order to produce hot water. Experimental results are presented along with relevant system operational parameters for appropriate operation including natural gas consumption, net electrical and thermal power production, i.e., hot and cold water production rates, primary energy saving index, and the energy utilization factor over total and partial electrical load operational conditions. (c) 2011 Elsevier Ltd. All rights reserved.

Engineering Active Pharmaceutical Ingredients by Spray Drying: Effects on Physical Properties and In Vitro Dissolution

Active pharmaceutical ingredients have very strict quality requirements; minor changes in the physical and chemical properties of pharmaceuticals can adversely affect the dissolution rate and therefore the bioavailability of a given drug. Accordingly, the aim of the present study was to investigate the effect of spray drying on the physical and in vitro dissolution properties of four different active pharmaceutical ingredients, namely carbamazepine, indomethacin, piroxicam, and nifedipine. Each drug was dispersed in a solution of ethanol and water (70:30) and subjected to single-step spray drying using similar operational conditions. A complete characterization of the spray-dried drugs was performed via differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), particle size distribution analysis, solubility analysis, and an in vitro dissolution study. The results from the thermal analysis and X-ray diffraction showed that, except for carbamazepine, no chemical modifications occurred as a result of spray drying. Moreover, the particle size distribution of all the spray-dried drugs significantly decreased. In addition, SEM images showed that most of the particles had an irregular shape. There was no significant improvement in the solubility of the spray-dried drugs compared with the unprocessed compounds; however, in general, the dissolution rates of the spray-dried drugs showed a remarkable improvement over their non-spray-dried counterparts. Therefore, the results from this study demonstrate that a single spray-drying step may lead to changes in the physical properties and dissolution characteristics of drugs and thus improve their therapeutic action.

Physico-chemical, spectroscopical and thermal characterization of biodiesel obtained by enzymatic route as a tool to select the most efficient immobilized lipase

Two microbial lipases from Burkholderia cepacia and Pseudomonas fluorescens were evaluated as catalysts for the enzymatic transesterification of beef tallow with ethanol and the most efficient lipase source was selected by taking into account the properties of the product to be used as fuel. Both lipases were immobilized on an epoxy silica-polyvinyl alcohol composite by covalent immobilization and used to perform the reactions under the following operational conditions: beef tallow-to-ethanol molar ratio of 1:9, 45ºC and 400 units of enzymatic activity per gram of fat. Products, characterized using Fourier Transform Infrared spectroscopy (FTIR), viscosimetry, thermogravimetry and ¹H NMR spectroscopy, suggested that the biodiesel sample obtained in the reaction catalyzed by Burkholderia cepacia lipase has the best set of properties for fuel usage.

Biodegradazione aerobica cometabolica di cloroformio: studio di fattibilità in reattori a biomassa adesa

Chlorinated Aliphatic Hydrocarbons (CAHs) are widespread wastewater and groundwater contaminants and represent a real danger for human health and environment. This research is related to the biodegradation technologies to treat chlorinated hydrocarbons. In particular the study of this thesis is focused on chloroform cometabolism by a butane-grown aerobic pure culture (Rhodococcus aetherovorans BCP1) in continuous-flow biofilm reactors, which are used for in-situ and on-site treatments. The work was divided in two parts: in the first one an experimental study has been conducted in two packed-bed reactors (PBRs) for a period of 370 days; in the second one a fluid dynamics and kinetic model has been developed in order to simulate the experimental data concerning a previous study made in a 2-m continuous-flow sand-filled reactor. The goals of the first study were to obtain preliminary information on the feasibility of chloroform biodegradation by BCP1 under attached-cell conditions and to evaluate the applicability of the pulsed injection of growth substrate and oxygen to biofilm reactors. The pulsed feeding represents a tool to control the clogging and to ensure a long bioreactive zone. The operational conditions implemented in the PBRs allowed the attainment of a 4-fold increase of the ratio of chloroform degraded to substrate consumed, in comparison with the phase of continuous substrate supply. The second study was aimed at identifying guidelines for optimizing the oxygen/substrate supply schedule, developing a reliable model of chloroform cometabolism in porous media. The tested model led to a suitable interpretation of the experimental data as long as the ratio of CF degraded to butane consumed was ≤ 0.27 mgchloroform /mgbutane. A long-term simulation of the best-performing schedule of pulsed oxygen/substrate supply indicated the attainment of a steady state condition characterized by unsatisfactory bioremediation performances, evidencing the need for a further optimization of the pulsed injection technique.

Development of a biorefinery scheme for the valorization of olive mill wastewaters and grape pomaces

In the Mediterranean area, olive mill wastewater (OMW) and grape pomace (GP) are among the major agro-industrial wastes produced. These two wastes have a high organic load and high phytotoxicity. Thus, their disposal in the environment can lead to negative effects. Second-generation biorefineries are dedicated to the valorization of biowaste by the production of goods from such residual biomasses. This approach can combine bioremediation approaches to the generation of noble molecules, biomaterials and energy. The main aim of this thesis work was to study the anaerobic digestion of OMW and GP under different operational conditions to produce volatile fatti acids (VFAs) (first stage aim) and CH4 (second stage aim). To this end, a packed-bed biofilm reactor (PBBR) was set up to perform the anaerobic acidogenic digestion of the liquid dephenolized stream of OMW (OMWdeph). In parallel, the solid stream of OMW (OMWsolid), previously separated in order to allow the solid phase extraction of polyphenols, was addressed to anaerobic methanogenic digestion to obtain CH4. The latter experiment was performed in 100ml Pyrex bottles which were maintained at different temperatures (55-45-37°C). Together with previous experiments, the anaerobic acidogenic digestion of fermented GP (GPfreshacid) and dephenolized and fermented GP (GPdephacid) was performed in 100ml Pyrex bottles to estimate the concentration of VFAs achievable from each aforementioned GPs. Finally, the same matrices of GP and not pre-treated GP (GPfresh) were digested under anaerobic methanogenic condition to produce CH4. Anaerobic acidogenic and methanogenic digestion processes of GPs lasted about 33 days. Instead, the anaerobic acidogenic and methanogenic digestion process of OMWs lasted about 121 and 60 days, respectively. Each experiment was periodically monitored by analysing volume and composition of produced biogas and VFA concentration. Results showed that VFAs were produced in higher concentrations in GP compared to OMWdeph. The overall concentration of VFAs from GPfreshacid was approximately 39.5 gCOD L-1, 29 gCOD L-1 from GPdephacid, and 8.7 gCOD L-1 from OMWdeph. Concerning the CH4 production, the OMWsolid reached a high biochemical methane potential (BMP) at a thermophilic temperature (55°) than at mesophlic ones (37-45°C). The value reached was about 358.7 mlCH4 gSVsub-1. In contrast, GPfresh got a high BMP but at a mesophilic temperature. The BMP was about 207.3 mlCH4 gSVsub-1, followed by GPfreshacid with about 192.6 mlCH4 gSVsub-1 and lastly GPdephacid with about 102.2 mlCH4 gSVsub-1. In summary, based on the gathered results, GP seems to be a better carbon source for acidogenic and methanogenic microrganism compared to OMW, because higher amount of VFAs and CH4 were produced in AD of GP than OMW. In addition to these products, polyphenols were extracted by means of a solid phase extraction (SPE) procedure by another research group, and VFAs were utilised for biopolymers production, in particular polyhydroxyalkanoates (PHAs), by the same research group in which I was involved.

Development and validation of a real-time quantitative PCR assay for rapid identification of Bacillus anthracis in environmental samples

A real-time polymerase chain reaction (PCR) assay was developed for rapid identification of Bacillus anthracis in environmental samples. These samples often harbor Bacillus cereus bacteria closely related to B. anthracis, which may hinder its specific identification by resulting in false positive signals. The assay consists of two duplex real-time PCR: the first PCR allows amplification of a sequence specific of the B. cereus group (B. anthracis, B. cereus, Bacillus thuringiensis, Bacillus weihenstephanensis, Bacillus pseudomycoides, and Bacillus mycoides) within the phosphoenolpyruvate/sugar phosphotransferase system I gene and a B. anthracis specific single nucleotide polymorphism within the adenylosuccinate synthetase gene. The second real-time PCR assay targets the lethal factor gene from virulence plasmid pXO1 and the capsule synthesis gene from virulence plasmid pXO2. Specificity of the assay is enhanced by the use of minor groove binding probes and/or locked nucleic acids probes. The assay was validated on 304 bacterial strains including 37 B. anthracis, 67 B. cereus group, 54 strains of non-cereus group Bacillus, and 146 Gram-positive and Gram-negative bacteria strains. The assay was performed on various environmental samples spiked with B. anthracis or B. cereus spores. The assay allowed an accurate identification of B. anthracis in environmental samples. This study provides a rapid and reliable method for improving rapid identification of B. anthracis in field operational conditions.

Carbon dioxide sequestration in cement kiln dust through miner carbonation

The feasibility of carbon sequestration in cement kiln dust (CKD) was investigated in a series of batch and column experiments conducted under ambient temperature and pressure conditions. The significance of this work is the demonstration that alkaline wastes, such as CKD, are highly reactive with carbon dioxide (CO2). In the presence of water, CKD can sequester greater than 80% of its theoretical capacity for carbon without any amendments or modifications to the waste. Other mineral carbonation technologies for carbon sequestration rely on the use of mined mineral feedstocks as the source of oxides. The mining, pre-processing and reaction conditions needed to create favorable carbonation kinetics all require significant additions of energy to the system. Therefore, their actual net reduction in CO2 is uncertain. Many suitable alkaline wastes are produced at sites that also generate significant quantities of CO2. While independently, the reduction in CO2 emissions from mineral carbonation in CKD is small (~13% of process related emissions), when this technology is applied to similar wastes of other industries, the collective net reduction in emissions may be significant. The technical investigations presented in this dissertation progress from proof of feasibility through examination of the extent of sequestration in core samples taken from an aged CKD waste pile, to more fundamental batch and microscopy studies which analyze the rates and mechanisms controlling mineral carbonation reactions in a variety of fresh CKD types. Finally, the scale of the system was increased to assess the sequestration efficiency under more pilot or field-scale conditions and to clarify the importance of particle-scale processes under more dynamic (flowing gas) conditions. A comprehensive set of material characterization methods, including thermal analysis, Xray diffraction, and X-ray fluorescence, were used to confirm extents of carbonation and to better elucidate those compositional factors controlling the reactions. The results of these studies show that the rate of carbonation in CKD is controlled by the extent of carbonation. With increased degrees of conversion, particle-scale processes such as intraparticle diffusion and CaCO3 micropore precipitation patterns begin to limit the rate and possibly the extent of the reactions. Rates may also be influenced by the nature of the oxides participating in the reaction, slowing when the free or unbound oxides are consumed and reaction conditions shift towards the consumption of less reactive Ca species. While microscale processes and composition affects appear to be important at later times, the overall degrees of carbonation observed in the wastes were significant (> 80%), a majority of which occurs within the first 2 days of reaction. Under the operational conditions applied in this study, the degree of carbonation in CKD achieved in column-scale systems was comparable to those observed under ideal batch conditions. In addition, the similarity in sequestration performance among several different CKD waste types indicates that, aside from available oxide content, no compositional factors significantly hinder the ability of the waste to sequester CO2.

Finite element analysis on Titan STL3 OTR tires

Finite element tire modeling can be a challenging process, due to the overall complexities within the tire and the many variables that are required to produce capable predictive simulations. Utilizing tools from Abaqus finite element software, adequate predictive simulations that represent actual operational conditions can be made possible. Many variables that result from complex geometries and materials, multiple loading conditions, and surface contact can be incorporated into modeling simulations. This thesis outlines modeling practices used to conduct analysis on specific tire variants of the STL3 series OTR tire line, produced by Titan Tire. Finite element models were created to represent an inflated tire and rim assembly, supporting a 30,000 lb load while resting on a flat surface. Simulations were conducted with reinforcement belt cords at variable angles in order to understand how belt cord arrangement affects tire components and stiffness response.

Tritium clouds environmental impact in air into the Western Mediterranean Basin evaluation

The paper considers short-term releases of tritium (mainly but not only tritium hydride (HT)) to the atmosphere from a potential ITER-like fusion reactor located in the Mediterranean Basin and explores if the short range legal exposure limits are exceeded (both locally and downwind). For this, a coupled Lagrangian ECMWF/FLEXPART model has been used to follow real time releases of tritium. This tool was analyzed for nominal tritium operational conditions under selected incidental conditions to determine resultant local and Western Mediterranean effects, together with hourly observations of wind, to provide a short-range approximation of tritium cloud behavior. Since our results cannot be compared with radiological station measurements of tritium in air, we use the NORMTRI Gaussian model. We demonstrate an overestimation of the sequence of tritium concentrations in the atmosphere, close to the reactor, estimated with this model when compared with ECMWF/FLEXPART results. A Gaussian “mesoscale” qualification tool has been used to validate the ECMWF/FLEXPART for winter 2010/spring 2011 with a database of the HT plumes. It is considered that NORMTRI allows evaluation of tritium-in-air-plume patterns and its contribution to doses.

Importance of nuclear data uncertainties in criticality calculations

The aim of this paper is to study the importance of nuclear data uncertainties in the prediction of the uncertainties in keff for LWR (Light Water Reactor) unit-cells. The first part of this work is focused on the comparison of different sensitivity/uncertainty propagation methodologies based on TSUNAMI and MCNP codes; this study is undertaken for a fresh-fuel at different operational conditions. The second part of this work studies the burnup effect where the indirect contribution due to the uncertainty of the isotopic evolution is also analyzed.

Localization and Tracking in Energy-Constrained Networks with Dynamic Connectivity

Systems used for target localization, such as goods, individuals, or animals, commonly rely on operational means to meet the final application demands. However, what would happen if some means were powered up randomly by harvesting systems? And what if those devices not randomly powered had their duty cycles restricted? Under what conditions would such an operation be tolerable in localization services? What if the references provided by nodes in a tracking problem were distorted? Moreover, there is an underlying topic common to the previous questions regarding the transfer of conceptual models to reality in field tests: what challenges are faced upon deploying a localization network that integrates energy harvesting modules? The application scenario of the system studied is a traditional herding environment of semi domesticated reindeer (Rangifer tarandus tarandus) in northern Scandinavia. In these conditions, information on approximate locations of reindeer is as important as environmental preservation. Herders also need cost-effective devices capable of operating unattended in, sometimes, extreme weather conditions. The analyses developed are worthy not only for the specific application environment presented, but also because they may serve as an approach to performance of navigation systems in absence of reasonably accurate references like the ones of the Global Positioning System (GPS). A number of energy-harvesting solutions, like thermal and radio-frequency harvesting, do not commonly provide power beyond one milliwatt. When they do, battery buffers may be needed (as it happens with solar energy) which may raise costs and make systems more dependent on environmental temperatures. In general, given our problem, a harvesting system is needed that be capable of providing energy bursts of, at least, some milliwatts. Many works on localization problems assume that devices have certain capabilities to determine unknown locations based on range-based techniques or fingerprinting which cannot be assumed in the approach considered herein. The system presented is akin to range-free techniques, but goes to the extent of considering very low node densities: most range-free techniques are, therefore, not applicable. Animal localization, in particular, uses to be supported by accurate devices such as GPS collars which deplete batteries in, maximum, a few days. Such short-life solutions are not particularly desirable in the framework considered. In tracking, the challenge may times addressed aims at attaining high precision levels from complex reliable hardware and thorough processing techniques. One of the challenges in this Thesis is the use of equipment with just part of its facilities in permanent operation, which may yield high input noise levels in the form of distorted reference points. The solution presented integrates a kinetic harvesting module in some nodes which are expected to be a majority in the network. These modules are capable of providing power bursts of some milliwatts which suffice to meet node energy demands. The usage of harvesting modules in the aforementioned conditions makes the system less dependent on environmental temperatures as no batteries are used in nodes with harvesters--it may be also an advantage in economic terms. There is a second kind of nodes. They are battery powered (without kinetic energy harvesters), and are, therefore, dependent on temperature and battery replacements. In addition, their operation is constrained by duty cycles in order to extend node lifetime and, consequently, their autonomy. There is, in turn, a third type of nodes (hotspots) which can be static or mobile. They are also battery-powered, and are used to retrieve information from the network so that it is presented to users. The system operational chain starts at the kinetic-powered nodes broadcasting their own identifier. If an identifier is received at a battery-powered node, the latter stores it for its records. Later, as the recording node meets a hotspot, its full record of detections is transferred to the hotspot. Every detection registry comprises, at least, a node identifier and the position read from its GPS module by the battery-operated node previously to detection. The characteristics of the system presented make the aforementioned operation own certain particularities which are also studied. First, identifier transmissions are random as they depend on movements at kinetic modules--reindeer movements in our application. Not every movement suffices since it must overcome a certain energy threshold. Second, identifier transmissions may not be heard unless there is a battery-powered node in the surroundings. Third, battery-powered nodes do not poll continuously their GPS module, hence localization errors rise even more. Let's recall at this point that such behavior is tight to the aforementioned power saving policies to extend node lifetime. Last, some time is elapsed between the instant an identifier random transmission is detected and the moment the user is aware of such a detection: it takes some time to find a hotspot. Tracking is posed as a problem of a single kinetically-powered target and a population of battery-operated nodes with higher densities than before in localization. Since the latter provide their approximate positions as reference locations, the study is again focused on assessing the impact of such distorted references on performance. Unlike in localization, distance-estimation capabilities based on signal parameters are assumed in this problem. Three variants of the Kalman filter family are applied in this context: the regular Kalman filter, the alpha-beta filter, and the unscented Kalman filter. The study enclosed hereafter comprises both field tests and simulations. Field tests were used mainly to assess the challenges related to power supply and operation in extreme conditions as well as to model nodes and some aspects of their operation in the application scenario. These models are the basics of the simulations developed later. The overall system performance is analyzed according to three metrics: number of detections per kinetic node, accuracy, and latency. The links between these metrics and the operational conditions are also discussed and characterized statistically. Subsequently, such statistical characterization is used to forecast performance figures given specific operational parameters. In tracking, also studied via simulations, nonlinear relationships are found between accuracy and duty cycles and cluster sizes of battery-operated nodes. The solution presented may be more complex in terms of network structure than existing solutions based on GPS collars. However, its main gain lies on taking advantage of users' error tolerance to reduce costs and become more environmentally friendly by diminishing the potential amount of batteries that can be lost. Whether it is applicable or not depends ultimately on the conditions and requirements imposed by users' needs and operational environments, which is, as it has been explained, one of the topics of this Thesis.

A model for setting services on auxiliary bus lines under congestion

In this paper, a mathematical programming model and a heuristically derived solution is described to assist with the efficient planning of services for a set of auxiliary bus lines (a bus-bridging system) during disruptions of metro and rapid transit lines. The model can be considered static and takes into account the average flows of passengers over a given period of time (i.e., the peak morning traffic hour) Auxiliary bus services must accommodate very high demand levels, and the model presented is able to take into account the operation of a bus-bridging system under congested conditions. A general analysis of the congestion in public transportation lines is presented, and the results are applied to the design of a bus-bridging system. A nonlinear integer mathematical programming model and a suitable approximation of this model are then formulated. This approximated model can be solved by a heuristic procedure that has been shown to be computationally viable. The output of the model is as follows: (a) the number of bus units to assign to each of the candidate lines of the bus-bridging system; (b) the routes to be followed by users passengers of each of the origin–destination pairs; (c) the operational conditions of the components of the bus-bridging system, including the passenger load of each of the line segments, the degree of saturation of the bus stops relative to their bus input flows, the bus service times at bus stops and the passenger waiting times at bus stops. The model is able to take into account bounds with regard to the maximum number of passengers waiting at bus stops and the space available at bus stops for the queueing of bus units. This paper demonstrates the applicability of the model with two realistic test cases: a railway corridor in Madrid and a metro line in Barcelona Planificación de los servicios de lineas auxiliares de autobuses durante las incidencias de las redes de metro y cercanías. El modelo estudia el problema bajo condiciones de alta demanda y condiciones de congestión. El modelo no lineal resultante es resuelto mediante heurísticas que demuestran su utilidad. Se demuestran los resultados en dos corredores de las ciudades de Barcelona y Madrid.

Evaluation of damping properties of structural glass panes under impact loading

The latest technology and architectural trends have significantly improved the use of a large variety of glass products in construction which, in function of their own characteristocs, allow to design and calculate structural glass elements under safety conditions. This paper presents the evaluation and analysis of the damping properties of rectangular laminated glass plates of 1.938 m x 0.876 m with different thickness depending on the number of PVB interlayers arranged. By means of numerical simulation and experimental verification, using modal analysis, natural frequencies and damping of the glass plates were calculated, both under free boundary conditions and operational conditions for the impact test equipment used in the experimental program, as the European standard UNE-EN 12600:2003 specifies.