Studio di membrane a base di liquidi ionici per il trasporto facilitato di CO2

In questo lavoro viene effettuata un’analisi di membrane per la separazione di CO2 basate sul meccanismo di trasporto facilitato. Queste membrane sono caratterizzate da un supporto poroso impregnato di una fase liquida le cui proprietà chimico-fisiche vengono presentate in relazione alle performance di separazione fornite: si tratta di liquidi ionici che presentano gruppi funzionali in grado di reagire con la CO2 consentendo il trasporto facilitato del gas acido attraverso la membrana. Le prestazioni in termini di separazione di CO2 da miscele gas fornite da questa tecnologia vengono analizzate e confrontate con quelle offerte da altre tipologie di membrane: alcune basate sul meccanismo di solution-diffusion (membrane polimeriche e membrane impregnate di liquidi ionici room-temperature) ed altre caratterizzate da permeazione di CO2 con presenza di reazione chimica ottenuta mediante facilitatori (mobili o legati allo scheletro carbonioso del polimero costituente la membrana). I risultati ottenuti sono analizzati in merito alla possibile implementazione di tale sistema di separazione a membrana in processi di cattura di CO2 nell'ambito della tecnologia di Carbon Capture and Storage.

Thermodynamic efficiency of carbon capture and utilisation in anaerobic batch digestion process

Carbon capture and storage (CCS) in the oil and water industries is becoming common and a significant consumer of energy typically requiring 150–450 °C and or several hundred bar pressure [1] particularly in geological deposition. A biological carbon capture and conversion has been considered in conventional anaerobic digestion processes. The process has been utilised in biological mixed culture, where acetoclastic bacteria and hydrogenophilic methanogens play a major key role in the utilisation of carbon dioxide. However, the bio catalytic microorganisms, hydrogenophilic methanogens are reported to be unstable with acetoclastic bacteria. In this work the biochemical thermodynamic efficiency was investigated for the stabilisation of the microbial process in carbon capture and utilisation. The authors observed that a thermodynamic efficiency of biological carbon capture and utilisation (BCCU) had 32% of overall reduction in yield of carbon dioxide with complimentary increase of 30% in yield of methane, while the process was overall endothermic. Total consumption of energy (≈0.33 MJ l−1) was estimated for the carbonate solubility (0.1 mol l−1) in batched BCCU. This has a major influence on microbial composition in the bioreactor. This thermodynamic study is an essential tool to aid the understanding of the interactions between operating parameters and the mixed microbial culture.

Liquid-phase alcohol promoted methanol synthesis from CO2 and H2

Methanol is an important and versatile compound with various uses as a fuel and a feedstock chemical. Methanol is also a potential chemical energy carrier. Due to the fluctuating nature of renewable energy sources such as wind or solar, storage of energy is required to balance the varying supply and demand. Excess electrical energy generated at peak periods can be stored by using the energy in the production of chemical compounds. The conventional industrial production of methanol is based on the gas-phase synthesis from synthesis gas generated from fossil sources, primarily natural gas. Methanol can also be produced by hydrogenation of CO2. The production of methanol from CO2 captured from emission sources or even directly from the atmosphere would allow sustainable production based on a nearly limitless carbon source, while helping to reduce the increasing CO2 concentration in the atmosphere. Hydrogen for synthesis can be produced by electrolysis of water utilizing renewable electricity. A new liquid-phase methanol synthesis process has been proposed. In this process, a conventional methanol synthesis catalyst is mixed in suspension with a liquid alcohol solvent. The alcohol acts as a catalytic solvent by enabling a new reaction route, potentially allowing the synthesis of methanol at lower temperatures and pressures compared to conventional processes. For this thesis, the alcohol promoted liquid phase methanol synthesis process was tested at laboratory scale. Batch and semibatch reaction experiments were performed in an autoclave reactor, using a conventional Cu/ZnO catalyst and ethanol and 2-butanol as the alcoholic solvents. Experiments were performed at the pressure range of 30-60 bar and at temperatures of 160-200 °C. The productivity of methanol was found to increase with increasing pressure and temperature. In the studied process conditions a maximum volumetric productivity of 1.9 g of methanol per liter of solvent per hour was obtained, while the maximum catalyst specific productivity was found to be 40.2 g of methanol per kg of catalyst per hour. The productivity values are low compared to both industrial synthesis and to gas-phase synthesis from CO2. However, the reaction temperatures and pressures employed were lower compared to gas-phase processes. While the productivity is not high enough for large-scale industrial operation, the milder reaction conditions and simple operation could prove useful for small-scale operations. Finally, a preliminary design for an alcohol promoted, liquid-phase methanol synthesis process was created using the data obtained from the experiments. The demonstration scale process was scaled to an electrolyzer unit producing 1 Nm3 of hydrogen per hour. This Master’s thesis is closely connected to LUT REFLEX-platform.

Post-combustion CO2 adsorption on activated carbons with different textural properties

Fixed bed CO2 adsorption tests were carried out in model flue-gas streams onto two commercial activated carbons, namely Filtrasorb 400 and Nuchar RGC30, at 303 K, 323 K and 353 K. Thermodynamic adsorption results highlighted that the presence of a narrower micropore size distribution with a prevailing contribution of very small pore diameters, observed for Filtrasorb 400, is a key factor in determining a higher CO2 capture capacity, mostly at low temperature. These experimental evidences were also corroborated by the higher value of the isosteric heat derived for Filtrasorb 400, testifying stronger interactions with CO2 molecules with respect to Nuchar RGC30. Dynamic adsorption results on the investigated sorbents highlighted the important role played by both a greater contribution of mesopores and the presence of wider micropores for Nuchar RGC30 in establishing faster capture kinetics with respect to Filtrasorb 400, in particular at 303 K. Furthermore, the modeling analysis of 15% CO2 breakthrough curves allowed identifying intraparticle diffusion as the rate-determining step of the process.

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Analisi delle caratteristiche e delle performance di membrane polimeriche a microporosità intrinseca (PIM) per la cattura di CO2

In questo lavoro viene condotta un’analisi critica delle caratteristiche materiali e delle performance di una classe di polimeri recentemente sviluppata, i “Polimeri a Microporosità Intrinseca”, di grande interesse per lo sviluppo di membrane per la separazione di gas, specialmente nella Carbon Capture. Partendo dall’analisi del meccanismo di separazione di gas in membrane polimeriche dense si fornisce una overview sulle tecnologie assodate e innovative per la separazione di gas e per la CC. Le caratteristiche e le proprietà strutturali di rilievo dei polimeri vetrosi sono poi brevemente illustrate e le correlazioni empiriche note tra le suddette e le proprietà di trasporto di materia. Vengono quindi descritti i PIMs analizzando in primis la loro tipica struttura chimica, i processi di sintesi e le caratteristiche principali. Per il PIM-1, capostipite della categoria, il trasporto di gas viene approfondito con lo studio della variabilità delle proprietà quali la permeabilità, la diffusività e la solubilità di penetranti gassosi con i parametri operativi (p, T, composizione dei feed), considerando anche fenomeni tipici dei polimeri vetrosi quali l’aging e l’effetto dei solventi. Sono poi analizzate le proprietà di trasporto nei diversi PIMs, e confrontate con quelle di polimeri di comune utilizzo nelle separazioni in esame. La rielaborazione dei dati raccolti permette di confrontare le performance di una varietà di polimeri nella separazione di gas. In particolare l’analisi critica dei diagrammi permeabilità/selettività induce ad una valutazione approssimativa ma significativa delle possibili soluzioni tra cui optare per una data separazione di gas, considerando anche i parametri operativi tipici della stessa. Infine, vengono riportati e commentati dati di permeazione di miscele gassose in due diversi PIMs e nel polimero PTMSP, ponendo l’attenzione sulle reali condizioni operative con cui la tecnologia a membrane si deve confrontare in applicazioni reali.

Carbon aerogels used in carbon dioxide capture

In this work the maximum carbon dioxide adsorption capacity of carbon aerogels, obtained by a sol-gel process using 2,4-dihydroxybenzoic acid/formaldehyde (DHBAF) and resorcinol/formaldehyde (RF) as precursors, was studied. The effect of increasing the temperature of carbonization and physical activation of the samples DHBAF was also studied. The results showed that the maximum adsorption capacity is favoured at lower temperatures, adsorption and desorption are rapid and the performance is maintained over several cycles of CO2 adsorption/desorption. A comparison with samples of commercial carbons was also made and it was concluded that carbon aerogels exhibit a behaviour comparable or superior to that obtained for the commercial carbons studied.

Synthesis, Modification and Characterization of Polymeric Membranes for CO2 Separation

This doctorate focused on the development of dense polymeric membranes for carbon capture, mostly in post combustion applications, and for natural gas sweetening. The work was supported by the European Project NANOMEMC2 funded under H2020 program. Different materials have been investigated, that rely on two main transport mechanisms: the solution-diffusion and the facilitated transport. In both cases, proper nano-fillers have been added to the matrix, in order to boost the mechanical and permselective properties of the membranes. Facilitated transport membranes were based on the use of was polyvinylamine (PVAm), as main matrix with fixed-site carriers, and L-Arginine as mobile carrier; the filler, used mostly as reinforcer, was carboxymethylated nanocellulose (cNFC). Humid test showed interesting results, and especially the blend made of PVAm/cNFC/Arg in weight ratio 27,5/27,5/45 crossed the Robeson CO2/N2 upper bound, representing current state of the art membranes, with a CO2 permeability of 271 Barrer and CO2/N2 selectivity of 70. Solution diffusion membranes were based on Pebax®2533 matrix which was added with three different graphene oxide (GO)-based materials, namely pristine GO, Porous Graphene Oxide (PGO) and a GO functionalized with polyetheramine (PEAGO). All of them provided a modest but clear increment of permeability of the Pebax matrix, from plus 2% (GO) to plus 8% (PGO), with no change in selectivity. The gas tested with this type of composites were CO2 and N2, for Post combustion capture applications. Pebax®2533 was also chemically modified, obtaining the product called “Benzoyl-P2533”, that was fully characterized, and tested in term of permeation using five gas: CO2, N2, CH4, O2, and He. Modified material showed an increment of the overall permeability of the material of a fair 10% for all gases tested, apart from helium, that increased of almost 50%.

Adsorbimento dinamico di CO2 in compositi innovativi a base geopolimerica

Fra le alternative proposte per la riduzione delle emissioni di CO2, le tecniche di Carbon Capture si presentano come un’efficace soluzione per il breve e medio termine. Fra queste, l’adsorbimento su fase solida per la rimozione di CO2 da correnti gassose si prospetta come una valida alternativa rispetto al convenzionale assorbimento ad umido. Questo lavoro di tesi si è occupato della sintesi di un composito a base geopolimerica presso l’ISTEC/CNR di Faenza, da impiegare per l’adsorbimento di CO2 a bassa temperatura, e dell’analisi del suo comportamento in regime di adsorbimento dinamico. Tale materiale è stato sintetizzato tramite attivazione con soluzione alcalina di metacaolino 1200S addizionato con polveri di zeolite Na13X. Esso costituisce una opzione interessante per la cattura di CO2, mostrando capacità di adsorbimento superiori a 1 mmol/g per concentrazioni di CO2 del 14% (a pressione atmosferica), simili a quelle presenti in molti processi industriali. Le prestazioni in regime dinamico risultano inoltre simili a quelle registrate nel regime statico. Le prove sperimentali hanno evidenziato la criticità della rigenerazione del materiale, in particolare riguardo all’eliminazione dell’acqua. Una temperatura di 130°C si mostra adatta per ottenere un’elevata rigenerazione del materiale, con rimozione sia di CO2 che dell’umidità adsorbita. Dalle prove svolte è risultato evidente come non sia conveniente operare con desorbimenti a temperatura ambiente e pressione atmosferica, ma sia necessario operare combinando swing di pressione e temperatura. È stato inoltre valutato l’effetto di una più bassa temperatura di adsorbimento (2°C), che porta ad un aumento della capacità del materiale. Sviluppi futuri in questo campo potrebbero essere la produzione di monoliti geopolimerici a porosità strutturate tramite tecniche innovative quali il freeze-casting e l’utilizzo di compositi integrati con additivi che ne migliorino le performance in termini di conducibilità termica.

Studio della permeabilità di CO2 e N2 in membrane composite di Aquivion e PVAm

Per mitigare il notevole aumento di emissioni di gas serra, molti studi si stanno focalizzando sulle membrane a trasporto facilitato per la separazione e la cattura di CO2. In particolare, le tecnologie di Carbon Capture and Storage (CCS) hanno ridestato interesse basandosi principalmente sulla cattura dell’anidride carbonica. L’obiettivo di questo studio è stato di migliorare le prestazioni di selettività nell’Aquivion, membrana ionomerica dell’acido perfluorosolfonico. Gli ottimi valori di permeabilità che raggiunge hanno portato quindi a focalizzare le ricerche sul miglioramento della capacità selettiva tra CO2 e N2. Infatti, la permeabilità e la selettività sono considerati parametri di trade-off, all’aumento di uno corrisponde la diminuzione dell’altro. Inoltre, le buone prestazioni delle membrane a trasporto facilitato in presenza di gruppi amminici hanno portato al tentativo di associare ad un materiale come l’Aquivion, dalla buona conduttività protonica, la Polivinilammina. Le ammine in membrane a trasporto facilitato sono infatti in grado di legare selettivamente l’anidride carbonica. Il presente lavoro si è inizialmente focalizzato sulla purificazione della Polivinilammina e sull’accoppiamento delle due membrane. In seguito alla realizzazione, i film sono stati caratterizzati mediante spettroscopia FTIR-ATR e infine testati in condizioni di umidità con l’utilizzo di un permeometro. È infatti ampiamente studiato come migliorare la permeabilità dell’Aquivion all’aumentare dell’umidità. In conclusione, in condizioni di alta adesione della Polivinilammina all’Aquivion la selettività ad alte umidità è aumentata rispetto ai valori di letteratura in articoli condizioni.

Analisi delle conseguenze dei rilasci accidentali di CO2 dagli impianti di cattura e stoccaggio

Oggi si sta assistendo sempre più ad un consumo maggiore di energia, proveniente soprattutto da fonti fossili. Tuttavia, occorre evidenziare l’aspetto negativo correlato a tutto questo: l’incremento del rilascio di gas ad effetto serra, responsabili del fenomeno del surriscaldamento globale. La Carbon Capture, Utilisation and Storage (CCUS) è stata riconosciuta come tecnologia strategica per raggiungere l’obiettivo dell’azzeramento delle emissioni entro il 2050. Lo scopo della tesi è effettuare la valutazione delle conseguenze dei rilasci accidentali di CO2 dagli impianti di cattura, esprimendole in termini di distanze di danno per l’uomo e per le apparecchiature. Dopo il Capitolo 1, dal carattere introduttivo e in cui si spiega il perché si renda necessaria la cattura della CO2, il Capitolo 2 fornisce i valori di pericolosità della CO2 relativi agli effetti tossici e termici, in termini di concentrazioni e temperature soglia; inoltre, illustra i codici DNV PHAST, NIST FDS e Ansys FLUENT, utilizzati per effettuare la valutazione delle conseguenze. A seguire, il Capitolo 3 presenta un impianto di cattura della CO2 assunto come caso di studio, fornendo la descrizione del funzionamento dell’impianto e riportandone i documenti principali, quali il PFD e la mappa del layout. Inoltre, vengono individuati gli scenari di rilascio e sono specificate le condizioni ambientali considerate ai fini della modellazione della dispersione. Il Capitolo 4 riporta i risultati ottenuti dalle simulazioni effettuate con i software di modellazione illustrati nel Capitolo 2, effettuando un’analisi comparativa delle distanze di danno, corredata di un’ampia discussione. Il Capitolo 5, infine, riporta le considerazioni conclusive del lavoro di tesi e delinea alcuni possibili sviluppi futuri delle indagini.

Effect Of Daily Use Of An Enzymatic Denture Cleanser On Candida Albicans Biofilms Formed On Polyamide And Poly(methyl Methacrylate) Resins: An In Vitro Study.

Candida biofilms on denture surfaces are substantially reduced after a single immersion in denture cleanser. However, whether this effect is maintained when dentures are immersed in cleanser daily is unclear. The purpose of this study was to evaluate the effect of the daily use of enzymatic cleanser on Candida albicans biofilms on denture base materials. The surfaces of polyamide and poly(methyl methacrylate) resin specimens (n=54) were standardized and divided into 12 groups (n=9 per group), according to study factors (material type, treatment type, and periods of treatment). Candida albicans biofilms were allowed to form over 72 hours, after which the specimens were treated with enzymatic cleanser once daily for 1, 4, or 7 days. Thereafter, residual biofilm was ultrasonically removed and analyzed for viable cells (colony forming units/mm(2)) and enzymatic activity (phospholipase, aspartyl-protease, and hemolysin). Factors that interfered with the response variables were analyzed by 3-way ANOVA with the Holm-Sidak multiple comparison method (α=.05). Polyamide resin presented more viable cells of Candida albicans (P<.001) for both the evaluated treatment types and periods. Although enzymatic cleansing significantly (P<.001) reduced viable cells, daily use did not maintain this reduction (P<.001). Phospholipase activity significantly increased with time (P<.001) for both materials and treatments. However, poly(methyl methacrylate) based resin (P<.001) and enzymatic cleansing treatment (P<.001) contributed to lower phospholipase activity. Aspartyl-protease and hemolysin activities were not influenced by study factors (P>.05). Although daily use of an enzymatic cleanser reduced the number of viable cells and phospholipase activity, this treatment was not effective against residual biofilm over time.

Enzymatic Biodiesel Synthesis From Yeast Oil Using Immobilized Recombinant Rhizopus Oryzae Lipase.

The recombinant Rhizopus oryzae lipase (1-3 positional selective), immobilized on Relizyme OD403, has been applied to the production of biodiesel using single cell oil from Candida sp. LEB-M3 growing on glycerol from biodiesel process. The composition of microbial oil is quite similar in terms of saponifiable lipids than olive oil, although with a higher amount of saturated fatty acids. The reaction was carried out in a solvent system, and n-hexane showed the best performance in terms of yield and easy recovery. The strategy selected for acyl acceptor addition was a stepwise methanol addition using crude and neutralized single cell oil, olive oil and oleic acid as substrates. A FAMEs yield of 40.6% was obtained with microbial oils lower than olive oil 54.3%. Finally in terms of stability, only a lost about 30% after 6 reutilizations were achieved.

Nature-inspired Enzymatic Cascades To Build Valuable Compounds.

Biocatalysis currently is focusing on enzymatic and multi-enzymatic cascade processes instead of single steps imbedded into chemical pathways. Alongside this scientific revolution, this review provides an overview on multi-enzymatic cascades that are responsible for the biosynthesis of some terpenes, alkaloids and polyethers, which are important classes of natural products. Herein, we illustrate the development of studies inspired by multi- and chemo-enzymatic approaches to build the core moieties of polyethers, polypeptide alkaloids, piperidines and pyrrolidines promoted by the joint action of oxidoreductases, hydrolases, cyclases, transaminases and imine reductases.

Separation Of Glycosidic Catiomers By Twim-ms Using Co2 As A Drift Gas.

Traveling wave ion mobility mass spectrometry (TWIM-MS) is shown to be able to separate and characterize several isomeric forms of diterpene glycosides stevioside (Stv) and rebaudioside A (RebA) that are cationized by Na(+) and K(+) at different sites. Determination and characterization of these coexisting isomeric species, herein termed catiomers, arising from cationization at different and highly competitive coordinating sites, is particularly challenging for glycosides. To achieve this goal, the advantage of using CO2 as a more massive and polarizable drift gas, over N2 , was demonstrated. Post-TWIM-MS/MS experiments were used to confirm the separation. Optimization of the possible geometries and cross-sectional calculations for mobility peak assignments were also performed. Copyright © 2015 John Wiley & Sons, Ltd.