Dipartimento di Ingegneria dell'Ambiente - Tesi di Dottorato

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Questa collezione raccoglie le Tesi di Dottorato afferenti al Dipartimento di Ingegneria per l'Ambiente e il Territorio e Ingegneria Chimica dell'Università della Calabria.

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    Functionalized polymeric membranes for development of biohybrid systems
    (2016-02-26) Vitola, Giuseppe; Giorno, Lidietta; Drioli, Enrico; Molinari, Raffaele
    Le proprietà di superficie di una membrana sono di grande importanza per la sua funzione. Mediante tecniche di funzionalizzazione chimica è possibile ottenere membrane con gruppi funzionali in grado di adempiere nuove e diverse funzioni che rendono la membrana funzionalizzata un dispositivo in grado di svolgere funzioni multiple trovando applicazione in vari impieghi. Le membrane funzionalizzate, infatti, trovano impiego nei processi di separazione, nei settori che richiedono l’uso di membrane biocompatibili, e nell’immobilizzazione di biomolecole che a sua volta trova applicazione nella preparazione di biosensori e bioreattori a membrana. Questi ultimi sono particolarmente interessanti poiché sfruttano l’alta superficie specifica della membrana e permettono di integrare il processo di separazione con quello catalitico. Il presente lavoro di tesi ha riguardato lo sviluppo di membrane polimeriche biofunzionalizzate per la decontaminazione di acque da sostanze tossiche quali i pesticidi organofosfati. Il lavoro è stato focalizzato sullo studio di diverse tecniche per l’ingegnerizzazione di membrane polimeriche aventi differenti caratteristiche chimico-fisiche. L’impatto dei diversi tipi di funzionalizzazione è stato valutato considerando il grado di legame e le proprietà catalitiche di biomolecole immobilizzate sulle membrane funzionalizzate. I polimeri utilizzati per l’immobilizzazione delle biomolecole sono stati il fluoruro di polivinilidene (PVDF) e il polietersulfone (PES), materiali ampiamente usati in sistemi di filtrazione. La proteina sieroalbumina bovina (BSA) e l’enzima lipasi da candida rugosa (LCR) sono state selezionate quali biomolecole modello per lo studio della capacità di legame e le proprietà catalitiche delle membrane ingegnerizzate. Le condizioni ottimali di funzionalizzazione e immobilizzazione sono state poi impiegate per lo sviluppo di sistemi bioibridi contenenti l’enzima fosfotriesterasi (PTE), un enzima in grado di operare la detossificazione di organofosfati. Al fine di migliorare le performance degli enzimi immobilizzati sul PVDF è stato sviluppato un nuovo approccio di ingegnerizzazione. Esso ha riguardato la sintesi di nanoparticelle colloidali a base di poliacrilammide e il loro utilizzo, dopo opportuna funzionalizzazione, come vettori per l’immobilizzazione covalente di enzimi sul PVDF. La nuova strategia di immobilizzazione ha permesso di mantenere il microambiente idrofilo a livello dell’enzima immobilizzato migliorandone di conseguenza le proprietà catalitiche. La strategia allo stesso tempo ha consentito di preservare l’idrofobicità della membrana. Tale proprietà è necessaria per lo sviluppo di sistemi operanti nella decontaminazione di aria. I risultati hanno mostrato che l’enzima fosfotriesterasi immobilizzato sul PES mantiene un’attività residua maggiore rispetto a quella dell’enzima immobilizzato sul PVDF. La membrana biocatalitica in PES è risultata idonea per la decontaminazione di organofosfati in fare acquosa.
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    Evaluation of thermal polarization and membrane characteristics for membrane distillation
    (2014-11-11) Alì, Aamer; Drioli, Enrico; Aimar, Pierre; Bouzek, Karel; Fila, Vlastimil; Molinari, Raffaele
    The current PhD work emphasizes on various aspects of membrane distillation for approaching zero liquid discharge in seawater desalination. In broader sense, two themes have been discussed in detail: (i) correlation between membrane features and their performance in MD (ii) understanding and control of thermal polarization in MD. Introduction and state-of-the-art studies of MD including progress in membrane development, understanding the transport phenomenon, recent developments in module fabrication, fouling and related phenomenon and innovative applications have been discussed in introductory part of the thesis. The effect of operating conditions and dope compositions on membrane characteristics and correlation between membrane features and their performance has been discussed in subsequent section. It has been established that membrane morphology plays a crucial role in performance of the membrane for real applications. Furthermore, it has been demonstrated that the effect of membrane morphology is different for direct contact and vacuum configurations. Theoretical and experimental aspects of thermal polarization in direct contact membrane distillation have also been investigated. Thermal polarization phenomenon in a flat sheet membrane has been studied by using a specifically designed cell. The effect of operating conditions and solution concentration on thermal polarization has been explored experimentally. It has been observed that increased solution concentration favors the thermal polarization due to resulting poor hydrodynamic at the membrane surface and increase in diffusion resistance to the water vapors migrating from bulk feed phase to the membrane surface. Some active and passive techniques to decrease thermal polarization and possible fouling in membrane distillation have also been discussed in the current study. Thermal polarization can be greatly reduced by inducing secondary flows in the fluid flowing inside the fiber. The induction of secondary flows in the current study has been realized by using the fibers twisted in helical and wavy configurations. Due to improvement of thermal polarization coefficient on up and downstream, the undulating fiber geometries provide high flux and superior performance ratio. Application of intermittent and pulsatile flow to control thermal polarization in MD has also been discussed. It has been inferred that these flows have positive impact on performance ratio and volume based enhancement factors without compromising on packing density of the system. The application of MD for treatment of produced water has also been studied. The effect of membrane features on their performance for the treatment of this complex solution has been discussed. The desirable membrane features for successful application of MD for such treatment have been distinguished. It has been inferred that MD possesses the capability to produce a distillate of excellent quality and is an interesting candidate to recover the minerals present in the produced water. The fouling tendency of the membranes with different characteristics towards different types of feed solutions has also been discussed in this study. It has been shown that the porosity enhanced through the introduction of macrovoids in non-solvent induced phase separation technique creates problems related with wetting and pore scaling during practical application of such membranes. The fouling related issues are less severe in the membranes with sponge like microstructure but the overall porosity of such membranes is relatively less. Thus it has been concluded that there should be an optimum between the high throughput and stable performance of the membranes synthesized through phase inversion techniques. Conclusions of the study and future perspectives have been discussed in the last section of the study.
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    Development of membrane bioreactor (MBR) process applying novel low fouling membranes
    (2013-11-12) Deowan, Shamim Ahmed; Drioli, Enrico; Molinari, Raffaele; Figoli, Alberto; Hoinkis, Jan
    Water is a part and parcel of human life. Water contaminated from industry and agriculture with heavy metal ions, pesticides, organic compounds, endocrine disruptive compounds, nutrients (phosphates, nitrates, nitrites) has to be effi-ciently treated to protect humans from being intoxicated with these compounds or with bacteria. Clean water as basis for health and good living conditions is too far out of reach for the majority of the population in the world (Bionexgen, 2013). Water recycling is now widely accepted as a sustainable option to re-spond to the general increase of the fresh water demand, water shortages and for environmental protection. Water recycling is commonly seen as one of the main options to provide remedy for water shortage caused by the increase of the water demand and draughts as well as a response to some economical and environmental drivers. The main options for wastewater recycling are industri-al, irrigation, aquifer recharge and urban reuse (Pidou, M., 2006). Among the industrial wastewaters, the textile industry is long regarded as a water intensive sector, due to its high demand of water for all parts of its pro-cedures. Accordingly, textile wastewater includes quite a large variety of con-tents, chemicals, additives and different kinds of dyestuffs. The main environ-mental concern with this waste water is about the quantity and quality of the water discharged and the chemical load it carries. To illustrate, for each ton of fabric products, 20 – 350 m3 of water are consumed, which differs from the color and procedure used. The quality of the textile wastewater depends much on the employed coloring matters, dyestuffs, accompanying chemicals, as well as the process itself (Brik et al., 2006). MBR technology is recognised as a promising technology to provide water with reliable quality for reuse. It provides safely reuse water for non-potable use. But the treated textile wastewater by MBR technology alone can’t comply with the reuse or discharge standard in many countries due to its colouring matters and dyestuffs remained in the effluent, if otherwise, MBR is associated with other technology like NF, RO, other processes or the applied membrane is modified or a novel MBR is applied. Fouling is another limiting factor for worldwide application of MBR technology especially in high-strength industri-al wastewater like textile wastewater. Moreover, membrane fouling is regarded as the most important bottleneck for further development of MBR technology. It is the main limitation for faster development of this process, particularly when it leads to flux losses that cleaning cannot restore (Howell et al. 2004). In this thesis work, a novel membrane bioreactor (MBR) process was devel-oped by modifying a applied commercial PES UF membrane in MBR module by nano-structured novel coating through polymerisable bicontinuous micro-emulsion (PBM) process with the purpose of having higher hydrophilicity and low fouling propensity. Before starting the MBR experiments, some characteri-sation tests such as SEM, AFM images analysis, roughness measurements, pore geometry, contact angel, standard salt rejections, model textile dye rejec-tions were performed. In addition, fouling tests using two laboratory cross flow testing units were conducted as well. To reach the ultimate goal of research, 6 sheets of novel coated membranes with size of 30 cm × 30 cm were prepared and these were used to prepare a three-envelope MBR module of 25 cm × 25 cm in size (total membrane area 0.33 m2) similar to that of a commercially available three-envelope PES UF MBR module. This novel MBR module was tested in a submerged lab-scale MBR pilot plant (tank volume ca. 60 L) for about 6 months using model textile dye wastewater (MTDW) as test media for all experiments with the aim of having uniform compositions with respect to time. The tests were done based on carefully selected operation conditions. Prior to testing of the novel membrane module MBR, experiments were carried out with a commercial PES UF MBR module using the same pilot plant set up and the same selected operating conditions for about 10 months. After comple-tion of trials with the novel coated MBR module, similar experiments were carried out again with a commercial PES UF MBR module to check the simi-larity of the biological sludge conditions and other operation conditions as well. In short, the sequences of the experiments were as follows: Commercial PES UF MBR (10 months) →novel membrane coated MBR (6 months)→PES UF MBR (1.5 months) The ultimate goal of the experiments was to compare the results between the commercial MBR and novel coated MBR module in order to demonstrate im-provement regarding fouling propensity and permeate water quality. The performance analysis shows that the novel coated MBR module compared to the commercial MBR module has 7% points higher COD removal efficien-cy, 20% points higher blue dye removal efficiency, high antifoul-ing/antimicrobial properties, resulting in a very low-fluctuating and highly ro-bust MBR process which looks promising with regard to economic viability. Since the newly developed MBR module worked excellent on laboratory scale it consequently should be deployed at an industrial site to be tested with real ii wastewater. Therefore, this novel three-envelope MBR module is on the way to be tested with real wastewater in a textile factory in Tunisia. The findings of these on-site pilot trials will serve as a basis for further improvement and even-tually pilot trails with larger membrane area will be addressed
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    Membrane Emulsification to develop biohybrid microstructured and multifunctional systems
    (2009-11-13) Piacentini, Emma; Drioli, Enrico; Molinari, Raffaele; Giorno, Lidietta
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    Process innovation and process intensification by membrane systems in the treatment of gas industrial streams
    (2014-06-10) Chiappetta, Giovanni; Drioli, Enrico; Barbieri, Giuseppe; Molinari, Raffaele