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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Preparation and Characterisation of Photocatalysts for CO2 valorisation in Membrane Reactors
(2019-05-10) Pomilla, Francesca Rita; Marcì, Giuseppe; Barbieri, Giuseppe; Molinari, Raffaele
Carbon dioxide is a gas that is constantly exchanged among the atmosphere, oceans, and land surface due to its continuous production and absorption by many microorganisms, plants and animals. These processes tend to balance the CO2 content in the atmosphere; however, since the Industrial Revolution, human activities are perturbing this equilibrium causing global warming and climate change. Due to this problem, an increasing concern has bring the scientific community to devote huge efforts to the CO2 reduction and/or valorisation. The published researches demonstrate that photocatalytic reduction of CO2 in the presence of H2O as reductant is a promising green way to obtain CH4, CO, CH3OH, EtOH, HCHO, acetaldehyde, and other products. Albeit, some aspects should be still improved in the use of the current technology, mainly related to the fact that TiO2, the most known photocatalyst, absorbs light in the ultraviolet region of the electromagnetic spectrum and the use of the visible light is by far desirable. Beside the use of the best light source, also the high recombination hole-electron photogenerated charges (h+ e-) should be reduced or, in the best prospective, suppressed. The aim of the current PhD dissertation is the CO2 reduction by renewable methods, by using sunlight in order to obtain molecules that eventually could be used as fuels. This challenge aims to miming the natural process
Preparation and Characterisation of Photocatalysts for CO2 valorisation in Membrane Reactors
(2019-05-10) Pomilla, Francesca Rita; Critelli, Salvatore; Marcì, Giuseppe; Barbieri, Giuseppe; Molinari, Raffaele
Modelling study of vanadium based alloys and crystalline porous materials for gas separation membranes
(2016-02-26) Borisova Evtimova, Jenny; De Luca, Giorgio; Curcio, Efrem; Molinari, Raffaele
Gas! membrane! separation! is! an! attractive! technology! that! is! often! superior! to! other! more! conventional! procedures! for! separation! of! gaseous! species! in! terms! of! energy! consumption! and! environmental! impact.! A! key! factor! for! membrane! separations! is! the! membrane! itself! with! its! properties,! which! determine! the! overall! performance! of! the! process.! One! essential! membrane! characteristic!is!the!transport!selectivity.!High!separation!factors!are!especially!difficult!to!achieve! for! mixtures! of! light! gases! having! comparable! kinetic! diameters.! Moreover,! high! permeability,! correspondingly! high! solubility! and! diffusivity! in! dense!membranes,! are! crucial! aspects! for! the! performance! and! further! practical! application! of!membrane! devices.! In! this! frame,! the!material! used!as!a!selective!layer!is!determinant.!Therefore,!scientists!devote!immense!efforts!to!the!search! of! optimal! gasBsorbent! combinations,! including! thorough! study! of! existing! structures! and! elaboration!of!new!ones!with!sieving!properties.!The!large!effort!and!time!required!for!preparation! and!experimental!testing!of!materials!impede!the!advancement!of!new!membranes.! In!this!study,!we!propose!procedures!based!on!computational!calculations!and!theoretical!models! that! can!be!used! to!predict! the!behaviour!of! some!of! the!membrane!materials!of! interest! for! gas! separation! applications.! In! particular,! we! focus! on:! i)! bodyBcentred! cubic! VNiTi! alloys! as! novel! materials!for!H2Bselective!dense!membranes!and!ii)!crystalline!porous!materials!that!are!attractive! media!for!separation!of!light!gases!such!as!H2,!O2,!CO,!CO2,!CH4!and!N2.!These!two!types!of!materials! are! treated! using! different! methodologies,! adapted! to! the! needs! of! our! research! objectives! associated!to!each!material.! In!the!case!of!dense!metal!membranes,!the!long!standingBcontroversy!over!occupancy!of!interstitial! hydrogen! in! VBbased! alloys! is! addressed.! The! VBNiBTi! system! is! of! particular! interest! here,! exhibiting!high!H2!permeability!and!improved!mechanical!properties!relative!to!pure!V.!This!work! intends!to!gain!understanding!of!hydrogenBmetal!interactions!as!function!of!alloy!composition!and! thereby!to!optimize!these!new!materials!and!advance!their!development!as!novel!membranes!for! H2! separation.!We! use! a! firstBprinciples! approach! that! gives! insights! into! the! sites! preference! of! hydrogen! and! assesses! the! role! of! Ti! and! Ni! substitutional! solutes! for! the! hydrogen! absorption! affinity.! The!method! based! on!Density! Functional! Theory! requires! no! experimental! input! except! crystal!structure!information.!Furthermore,!it!uses!no!empirical!or!fitting!parameters!in!contrast!to! other!computational!techniques.!Hence!this!approach!provides!an!alternative!way!to!explore!new! metal!alloys!for!H2!separation!membranes.!The!applied!methodology!can!be!used!further!in!highB throughput!calculations!to!screen!various! alloy!compositions.!The!heretoBreported!results!will!be! used!as!guidance!for!tailoring!the!formulation!of!VNiTi!solid!solutions!and!preparation!of!low!cost†! dense!alloy!membranes!in!the!frame!of!other!projects!(e.g.!European!DEMCAMER!project).! Further,! we! explore! how! singleBcomponent! inputs! can! be! used! to! forecast! the! ideal! selectivity! towards! light! gases! of! crystalline! porous!materials,! used! for!membrane! preparation.! Theoretical! models! for! describing! gas! separation! properties! of! zeotype! materials! as! function! of! structural! characteristics!and!operation!conditions!are!proposed.!The!model!parameters!can!be!obtained!as! experimentally!as!well!as!computationally.!To!analyse!the!extent!of!validity!and!limitations!of!the! models,!ideal!selectivities!of!few!crystalline!porous!materials!are!evaluated,!including!widely!used! zeolites!(NaA,!CaA)!and!a!metal!organic!framework!structure!(ZIFB8).!The!results!verified!that!the! theoretical!expressions!could!be!used!for!screening!series!of!zeotype!materials!when!reliable!single! gas!adsorption!data!are!available.!However,!since!the!models!don’t!take!into!account!all!parameters! (namely! related! to! the! membrane! design)! and! mechanisms! involved! in! gas! transport! through! porous!membranes,!their!predictions!should!be!considered!as!values!referring!to!an!ideal!case.!
Renewable energy generation and hydrogen production from concentrated brine by reverse eectrodialysis
(2016-02-26) Tufa, Ramato Ashu; Drioli, Enrico; Curcio, Efrem; Molinari, Raffaele
Salinity Gradient Power-Reverse Electrodialysis (SGP-RE) is among the emerging membrane-based technologies for renewable energy generation. In RE, cation exchange membranes (CEM) and anion exchange membranes (AEMs) are alternatively aligned to create a high concentration compartment (HCC) and low concentration compartment (LCC). When the compartments are feed by a low concentration and high concentration solution, salinity gradient is created which initiates the diffusive flux of ions towards electrodes. Electricity is generated by the redox process occurring at the electrodes. The total voltage generated (open circuit voltage, OCV) is proportional to the number of membrane pairs (cells). One of the challenges pertaining to the Ohmic losses when using very low concentration salt solutions like river water can be reduced by working with highly concentrated brines (Chapter 1). Investigation of the performance of RE under realistic high-salinity conditions is crucial for implementation of RE under natural condition. The most abundant ions in natural waters involve sodium, magnesium, calcium, chloride, sulfate, and bicarbonate. Under this condition, the presence of multivalent ions, in particular Mg2+, have a lowering effect on OCV and hence a reduction of power density. This could be attributed to the enhancement of cell resistance in the presence Mg2+ ion resulting in an increase of membrane resistance. The SGP potential and comparable decrease in power density of RE operated with solutions mimicking real brackish water and exhaust brine from a solar pond depicts the pretreatment requirement in RE for better performance (Chapter 2). Seawater reverse osmosis (SWRO) is the most widespread technology for fresh water production in many parts of the world. Extensive research have been carried out to tackle the technological challenges coming along with the expansion of SWRO practice with time, specifically the reduction of energy consumption. The integrated application RE in desalination technologies in the logic of process intensification is an interesting approach towards low energy desalination. Simultaneous production of energy and desalted water is possible by hybrid application of Direct Contact Membrane Distillation (DCMD) and RE units operated on the retentate stream from a SWRO desalination plant. The use of concentrated brine for energy recovery also leads to Near-Zero Liquid Discharge from desalination systems. This avoids the adverse ecological effect of discharging hypersaline solution into natural water bodies. Thus, integrated application of RE with RO and DCMD for simultaneous water and energy production represent an innovative approach towards low energy desalination and Near-Zero Liquid Discharge paradigm (Chapter 3). The possibilitity to exploit the chemical potential of sulfate wastes by SGP-RE can be a promising alternative renewable energy source. The key challenge remains the property of membrane in sulphate solution. Although the trends in the variation of desirable membrane properties (high permselectivity and low resistance) in Na2SO4 test solutions with varying operating conditions remain similar with that of NaCl test solution, their performance is comparatively low. This has a negative impact on the performance of the RE mainly on the obtained OCV and power density. Hence, design of well optimized and high performance membranes is required for practical applicability of SGP-RE for renewable energy generation from sulfate bearing waste resources (Chapter 4). Ion exchanging membranes (IEMs) are key components in RE. Low resistance and highly permeable ion exchange membranes are required for optimal performance of RE system. For practical applications of RE under real condition, IEMs which are less susceptible to fouling are required. There is a potential risk of fouling (for example, scaling of sparingly soluble salts) of IEM operated in concentrated brine. Operations under real conditions also require feed quality control, as the presence of multivalent ions negatively impact RE performance. The variation in Total Organic Carbon (TOC) and Total Hardness (TH) of feed samples may alter the membranes physico-chemical and electrochemical properties. In addition, long term stability of IEMs in concentrated brine govern their life time. Investigation on fouling and stability of IEMS, specifically in concentrated brines, would be essential to set a clear pretreatment requirement for the performance of RE under natural conditions (Chapter 5). For techno-economic optimization and feasibility study of RE, performance of large scale (industrial scale) systems need to be investigated under varying experimental conditions. Comparative assessment of operating conditions like feed concentration, flow velocity and temperature in a small scale RE and large scale RE systems is essential. In general, the trends in OCV and power density for industrial scale operations remain more or less similar to that of membrane based water and energy technologies (based on the difficulties to meet sustainability criteria) helps in identification of technological gaps and strategic solution (Chapter 9). Future research on RE will be focusing on optimal design and development of high performance membrane in hyper-saline solution. This will extend from design of highly permeable and low resistance ion exchange membranes to the development of fouling resistant and stable membrane, particularly in concentrated brine. The relationship between physicochemical membrane properties and fouling tendency under hyper-saline environment need to be assessed. The effect of other multivalent ions in seawater like SO4 2- and Ca2+ on the performance of RE under extreme operating conditions should be clearly outlined. For integrated applications in desalination technologies, for example with DCMD, the risk of scaling and fouling for practical applications should be investigated deeply. Better membranes and module designs are required for membrane desalination systems in general. For efficient application of RE in hydrogen technologies, specifically with APE water electrolysis, development of highly conductive and durable anion selective membranes as well as highly active and stable catalysts in corrosive alkaline environment is of future research interest. Above all, well established technoeconomic evaluations of a standalone and integrated applications of RE is essential in order to evaluate the feasibility of scale-up and commercialization of the technology as a renewable energy source (Chapter 10).
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.
Membrane crystallization for recovery of valuable compounds from waste streams
(2016-02-26) Quist-Jensen, Cejna Anna; Drioli, Enrico; Macedonio, Francesca; Molinari, Raffaele
Sustainable development and Process intensification strategy are guidelines for industrial processes in perspective. It is becoming more and more common that industry wants to fully exploit their resources due to environmental regulations, economic gain, sustainable standpoint, etc. In this perspective, waste streams have to be turned into resources in the most environmental friendly, economic and sustainable way. Membrane Engineering is already a key-figure to realize this objective. Novel membrane technologies such as membrane distillation (MD), membrane crystallization (MCr), pressure retarded osmosis (PRO), reverse electrodialysis (RED) and forward osmosis (FO), are evolving and are being suggested for a better exploitation of waste streams. This Ph.D. study focusses, particular, on Membrane crystallization (MCr), which is a novel technology for simultaneously production of water and minerals. It has several advantages with respect to conventional crystallizers in terms of purity, controlled kinetics and crystal morphology. Moreover, MCr is able to treat high concentration solutions, which are challenging for other traditional membrane operations. The current Ph.D. work emphasizes on various aspects of membrane crystallization for approaching zero-liquid discharge in industrial processes. Improved membranes, specifically developed for MCr applications, have to be manufactured. In this study, preliminary suggestions on membrane features are given for the requirements in MCr. Lab-made PVDF membranes with different characteristics have been tested and evaluated for their performance in MCr. This study, suggests that membranes with symmetric sponge layer structure and low thickness are favorable. Membrane of asymmetric structure with many macrovoids seems more pronounced to suffer from wetting. Moreover, it has been shown that, membrane crystallization is able to treat several kinds of feed solutions including RO brine, produced water and wastewater containing high amounts of sodium sulfate. The recovered crystals exhibit high purity, good size distribution and controlled growth. Na2SO4 can be recovered as different polymorphs and in this study it has been crystallized in the anhydrous form (Thenardite). Moreover, the process has shown excellent stability in terms of transmembrane flux and maintenance of hydrophobicity of the membrane. In some cases the treatment has been continued for more than 90 hours by only slight cleaning with distillate water. Membrane crystallization, in the direct-contact membrane distillation configuration, can normally treat solutions with very high concentrations. However, its limitations in the recovery of lithium from single salt solutions have been highlighted in this study. Vapor pressure, due to increase in concentration, is reduced significant, that it is not possible to reach LiCl saturation by this configuration. Likewise, combined direct-contact and osmotic distillation configuration have not been able to increase the driving force enough in order to exceed saturation. Instead vacuum membrane distillation has been introduced to eliminate the osmotic phenomena. This configuration has been able to recover LiCl in two different polymorph structures depending on the utilized operative conditions. Furthermore, integrated membrane system, including membrane crystallization, has shown excellent capability to treat orange juice. The quality of the juice has been maintained through ultrafiltration, membrane distillation and membrane crystallization treatment. In this study, the MD/MCr feed temperature is kept below 30 °C causing a relatively low flux. However, it has still been possible to reach from a concentration of 9 °brix to 65 °brix using MD/MCr. The advantages of MD/MCr with respect to isothermal osmotic membrane distillation configuration, is the elimination of the reconcentration stages of the draw solution. All the carried out case studies show that MD/MCr is able to reduce the volume of the waste stream significantly. The obtained results might be used as guidelines for practical application. Moreover, the low temperatures and atmospheric pressures utilized, makes it possible in real industrial processes to use waste or low-grade heat. Unlike other processes, MCr is able to produce two high quality products (i.e. water and salts) and will therefore not produce any additional waste. Hereby, the extended treatment by means of MCr will only positively influence the overall “sustainability” of the entire industrial process.
Chemical looping desulphurization: model and applications to power systems
(2016-02-26) Settino, Jessica; Molinari, Raffaele; Amelio, Mario
I processi di assorbimento, sia sici che chimici a base di ammine, sono attualmente utilizzati per rimuovere e cacemente i composti dello zolfo. Nonostante l'eccellente desolforazione, questa strategia e termicamente ine ciente, in quanto richiede gas a bassa temperatura. Scopo di questo lavoro e quello di analizzare soluzioni alternative che operino a temperature pi u elevate. A tale scopo, e stato analizzato il processo del chemical looping. Si tratta di una nuova tecnologia, in cui un materiale sorbente, in contatto con il gas combustibile grezzo, viene convertito nel suo solfuro e poi rigenerato cos da ricominciare il ciclo. Il sistema e costituito da due reattori: uno per la rigenerazione e l'altro per la desolforazione. Un modello matematico di tale sistema e stato sviluppato con il software Athena Visual Studio ed i suoi risultati confrontati con quelli ottenuti dal modello proposto dal National Energy Technology Laboratory, validati sulla base di dati sperimentali. Nella fase successiva, il sistema modellato e stato applicato a tre casi studio di interesse industriale: per la produzione di energia elettrica negli impianti a ciclo combinato con gassi cazione integrata, nei processi di metanazione, nei processi per la sintesi del metanolo. Mediante simulazioni, condotte con i software commerciali Thermo ex e UniSim Design, sono stati studiati gli e etti della desolforazione a caldo sulle prestazioni dei diversi sistemi.
Membrane emulsification for the development of particulate systems for drug encapsulation
(2014-11-11) Imbrogno, Alessandra; Giorno, Lidietta; Drioli, Enrico; Molinari, Raffaele
Il micro-incapsulamento è una tecnica ampiamente utilizzata per incapsulare sostanze nutraceutiche, farmaci, proteine, cellule ecc. Oggigiorno, la ricerca nel campo farmaceutico viene sempre più indirizzata allo sviluppo di forme farmaceutiche a rilascio modificato (ad esempio emulsioni multiple, sfere e capsule mono/ polinucleate) in grado di migliorare la biodisponibilità di principi attivi scarsamente solubili. La maggior parte delle metodologie utilizzate per la preparazione di particelle micro e nano-strutturate prevedono un processo iniziale di emulsificazione. In questo caso, il controllo della dimensione e dell’uniformità delle gocce è di fondamentale importanza per produrre particelle solide di dimensione controllata, da cui dipende la via di somministrazione, la distribuzione nei tessuti e l’interazione con le cellule. Negli ultimi 25 anni, enormi progressi sono stati realizzati nella preparazione di emulsioni con una dimensione controllata delle gocce grazie a un sempre più vasto utilizzo dell’emulsificazione a membrana, un processo vantaggioso rispetto alle tecniche convenzionali in termini di semplicità operativa, basso consumo energetico, alta riproducibilità e facile scale-up. L’aspetto innovativo di questo processo è la produzione delle gocce di emulsione singolarmente, ottenuta mediante permeazione della fase dispersa attraverso i pori della membrana, mentre il distacco della goccia avviene all’uscita del poro per effetto di uno sforzo di taglio esercitato dal fluire della fase continua. Un grande potenziale dell’emulsificazione a membrana per la preparazione di formulazioni farmaceutiche è la possibilità di combinare le proprietà chimiche della formulazione con le proprietà strutturali della particella (quali dimensione e dispersione) in modo da realizzare prodotti con caratteristiche funzionali idonee a specifiche applicazioni. Nella realizzazione di sistemi micro e nano-strutturati per l’incapsulamento di molecole bioattive, le proprietà chimico-fisiche del materiale sono anche di fondamentale importanza. Tra i materiali organici, i polimeri biodegradabili (in particolare il poli-caprolattone e il copolimero dell’acido lattico e glicolico) sono quelli di maggiore impiego in quanto offrono la possibilità di realizzare particelle che, una volta introdotte nell’organismo, vengono degradate in sottoprodotti metabolizzati dalle cellule. Questa proprietà conferisce a questi materiali un’eccellente biocompatibilità e il rilascio del farmaco incapsulato nelle particelle può essere modulato dalla velocità di degradazione del polimero. Inoltre questi polimeri sono idrofobi e quindi ideali per l’incapsulamento di farmaci insolubili in acqua, una procedura necessaria per poter essere somministrati nella circolazione sanguigna. Nonostante questi polimeri siano ampiamente utilizzati per la preparazione di sistemi micro e nano-strutturati, numerose problematiche sono state riscontrate nel controllo della dimensione e dispersione delle particelle e la loro morfologia. Lo scopo del presente lavoro di tesi è quello di utilizzare l’emulsificazione a membrana per la preparazione di sistemi micro e nano-strutturati utilizzabili per l’incapsulamento di farmaci idrofili e lipofili e realizzati con i polimeri biodegradabili precedentemente menzionati. Dall’analisi dello stato dell’arte sono stati individuati una serie di requisiti importanti per la preparazione di sistemi particellari: i) produrre particelle con dimensione e dispersione controllata utilizzando un processo ad alta produttività; ii) mantenere un basso stress meccanico per preservare l’attività delle sostanze incapsulate; iii) utilizzare un processo che può essere applicato su larga scala a livello industriale. La produzione di particelle altamente uniformi e con dimensione controllata mediante l’utilizzo dell’emulsificazione a membrana è già stato pienamente riportato in letteratura. Tuttavia, la possibilità di poter ottenere una produzione controllata dell’emulsione mantenendo allo stesso tempo un’alta produttività e un basso stress meccanico nell’impianto è tutt’ora oggetto di studio. Sulla base di queste osservazioni, gli avanzamenti proposti dal presente lavoro di tesi sono: • migliorare la produttività e l’efficienza del processo di emulsificazione a membrana mediante: i) l’utilizzo di una membrana con bagnabilità asimmetrica lungo la sezione al fine di mantenere allo stesso tempo una produzione controllata dell’emulsione ad un alto flusso di fase dispersa; ii) l’utilizzo di membrane di tipo “setaccio” in acciaio inox in modo da combinare i vantaggi delle caratteristiche strutturali della membrana setaccio (bassa porosità, basso spessore, pori rettilinei e uniformemente distribuiti) con l'elevata resistenza chimica dell’acciaio inossidabile, che è meno soggetto allo “sporcamento” per interazione con i componenti dell’emulsione; • indagare, inizialmente su piccola scala e poi con processi adatti per la produzione su larga scala, la preparazione di sistemi micro e nano particellari combinando la emulsificazione a membrana con il processo di diffusione del solvente per ottenere un controllo della dimensione e morfologia delle particelle in modo preciso e riproducibile rispetto all’ evaporazione del solvente comunemente utilizzata; • investigare l’utilizzo di processi di emulsificazione a membrana recentemente introdotti per applicazioni su larga scala, quali emulsificazione a membrana con flusso pulsato e invertito della fase continua ed emulsificazione a membrana con movimento torsionale della membrana, per la produzione di particelle micro e nano-strutturate in condizioni di basso stress meccanico e alta produttività del processo.
Bio-Hybrid Membrane Process for Food-based Wastewater Valorisation: a pathway to an efficient integrated membrane process design
(2014-11-11) Gebreyohannes, Abaynesh Yihdego; Giorno, Lidietta; Curcio, Efrem; Aimar, Pierre; Vankelecom, Ivo F.J.; Molinari, Raffaele
The food industry is by far the largest potable water consuming industry that releases about 500 million m3 of wastewater per annum with very high organic loading. Simple treatment of this stream using conventional technologies often fails due to cost factors overriding their pollution abating capacity. Hence, recently the focus has been largely centered on valorization through combinatorial recovery of valuable components and reclaiming good quality water using integrated membrane process. Membrane processes practically cover all existing and needed unit operations that are used in wastewater treatment facilities. They often come with advantages like simplicity, modularity, process or product novelty, improved competitiveness, and environmental friendliness. Thus, the main focus of this PhD thesis is development of integrated membrane process comprising microfiltration (MF), forward osmosis (FO), ultrafiltration (UF) and nanofiltration (NF) for valorization of food based wastewater within the logic of zero liquid discharge. As a case study, vegetation wastewater coming from olive oil production was taken. Challenges associated with the treatment of vegetation wastewater are: absence of unique hydraulic or organic loadings, presence of biophenolic compounds, sever membrane fouling and periodic release of large volume of wastewater. Especially presence of biophenolic compounds makes the wastewater detrimental to the environment. However, recovering these phytotoxic compounds can also add economic benefit to the simple treatment since they have interesting bioactivities that can be exploited in the food, pharmaceutical and cosmetic industries. The first part of the experimental work gives special emphasis on the development of biohybrid membranes used to control membrane fouling during MF. Regardless of 99% TSS removal with rough filtration, continuous MF of vegetation wastewater using 0.4 μm polyethelene membrane over 24 h resulted in continuous flux decline. This is due to sever membrane fouling mainly caused by macromolecules like pectins. To overcome the problem of membrane fouling, biocatalytic membrane reactors with covalently immobilized pectinase were used to develop self-cleaning MF membrane. The biocatalytic membrane with pectinase on its surface gave a 50% higher flux compared to its counterpart inert membrane. This better performance was attributed to simultaneous in-situ degradation of foulants and removal of hydrolysis products from reaction site that overcome enzyme product inhibition. Although the biocatalytic membrane gave a better performance, its fate is disposal once the covalently immobilized enzyme gets deactivated or oversaturated with foulants. To surmount this problem a new class of superparamagnetic biochemical membrane reactor was developed, verified and optimized. This development is novel for its use of superparamagnetic nanoparticles both as support for the immobilized enzyme and as agent to render the membrane magnetized. This reversible immobilization method was designed to facilitate the removal of enzyme during membrane cleaning using an external magnet. Hence PVDF based organic-inorganic (O/I) hybrid membrane was prepared using superparamagnetic nanoparticles (NPSP) as inorganic filler. In parallel, superparamagnetic biocatalytic nanocomposites were prepared by covalently immobilizing pectinase on to the surface of NPSP dispersed in aqueous media. The synergetic magnetic responsiveness of both the O/I hybrid membrane and the biocatalytic particle to an external magnetic field was later on used to physically immobilize the biocatalytic particles on the membrane. This magnetically controlled dynamic layer of biocatalytic particles prevented direct membrane-foulant interaction, allowed in-situ degradation, easy magnetic recovery of the enzyme from the surface of the membrane, use of both membrane and immobilized enzyme over multiple cycles and possibility of fresh enzyme make up. The system gave stable performance over broad range of experimental condition: 0.01-3 mg/mL foulant concentration, 1-9 g per m2 of membrane area bionanocomposites, 5- 45 L/m2.h flux and different filtration temperatures. Under condition of mass transfer rate prevailing reaction rate, the system gave upto 75% reduction in filtration resistance. After optimization of the different operational parameters, it also revealed no visible loss in enzyme activity or overall system performance, when 0.3 mg/mL pectin solution was continuously filtered for over two weeks. In addition, the chemical cleaning stability of the O/I hybrid membrane was studied under accelerated ageing and accelerated fouling conditions. The ageing caused change in the physicochemical characteristics and enhanced fouling propensity of the membrane due to step-by-step degradation of the polymeric coating layer of used NPSP. But 400 ppm NaOCl solution at pH 12 was found compatible; henceforth it was used to clean the membrane. Second major limitation identified during the treatment of vegetation wastewater is presence of large volume of wastewater that comes in short period following the harvest of olive fruit. To alleviate this problem, FO was investigated to concentrate the wastewater. This process is believed to be less energy demanding, suppose that draw solution does need to be regenerated, and with low foul propensity. By operating at 3.7 molal MgCl2 draw solution and 6 cm/s crossflow velocity, single-step FO resulted in an average flux of 5.2 kg/m2.h. and 71% volume concentration factor with almost complete retention of all the pollutants. Moreover, the system gave a stable performance over ten days when operated continuously. After FO, both NF and UF were used to fractionate the recovered biophenols from the concentrate streams of FO. Compared to polymeric UF membrane, ceramic NF gave better flux of 27 kg/m2.h at 200 L/h feed flow rate and 7 bar TMP. Finally, when FO was used as a final polishing step to recover highly concentrated biophenols from permeate of the UF; it gave an average flux of 5 kg/m2.h and VCF of 64%. In conclusion, a great success has been made in tackling the two most important challenges of vegetation wastewater valorisation using the concept of biohybridization and FO. The bioinspired NPSP provides strong evidence that magnetically controlled enzyme immobilization have an immense potential in membrane fouling prevention and paves a potential breakthrough for continuous wastewater filtration. By setting bio-inspired NPSP biocatalytic membrane reactor at the heart, it is possible to successfully use integrated membrane process for continuous valorisation of food based wastewater. In addition to fouling prevention, they open a new horizon for applications in localized biocatalysis to intensify performance in industrial production, processing, environmental remediation or bio-energy generation.
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.

Dipartimento di Ingegneria dell'Ambiente - Tesi di Dottorato

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