Studio ed ottimizzazione di processi per la produzione di membrane ceramiche per la separazione di idrogeno

Questa tesi descrive l’attività scientifica svolta presso l’istituto CNR-ISTEC di Faenza. Lo scopo è stato lo studio e l’ottimizzazione del processo per la realizzazione di una membrana ceramica permselettiva all’idrogeno usufruibile in applicazioni industriali. Grazie alle prove effettuate è stata possibile la realizzazione tramite colaggio su nastro dei due strati ceramici che formano la membrana: un supporto poroso e un film sottile e denso. I nastri, dopo essiccamento, sono stati tagliati con la geometria desiderata, impilati uno sull’altro, termocompressi e sinterizzati. L’attività svolta ha permesso l’ingegnerizzazione di una membrana ad elevato contenuto tecnologico con le proprietà necessarie per poter essere impiegata in un processo di purificazione di idrogeno più semplice, efficiente ed economico rispetto a quelli utilizzati fino ad ora.

Lung mechanics and gas exchange in ventilated preterm infants during treatment of hyaline membrane disease with multiple doses of artificial surfactant (Exosurf)

Eight premature infants ventilated for hyaline membrane disease and enrolled in the OSIRIS surfactant trial were studied. Lung mechanics, gas exchange [PaCO2, arterial/alveolar PO2 ratio (a/A ratio)], and ventilator settings were determined 20 minutes before and 20 minutes after the end of Exosurf instillation, and subsequently at 12-24 hour intervals. Respiratory system compliance (Crs) and resistance (Rrs) were measured by means of the single breath occlusion method. After surfactant instillation there were no significant immediate changes in PaCO2 (36 vs. 37 mmHg), a/A ratio (0.23 vs. 0.20), Crs (0.32 vs. 0.31 mL/cm H2O/kg), and Rrs (0.11 vs. 0.16 cmH2O/mL/s) (pooled data of 18 measurement pairs). During the clinical course, mean a/A ratio improved significantly each time from 0.17 (time 0) to 0.29 (time 12-13 hours), to 0.39 (time 24-36 hours) and to 0.60 (time 48-61 hours), although mean airway pressure was reduced substantially. Mean Crs increased significantly from 0.28 mL/cmH2O/kg (time 0) to 0.38 (time 12-13 hours), to 0.37 (time 24-38 hours), and to 0.52 (time 48-61 hours), whereas mean Rrs increased from 0.10 cm H2O/mL/s (time 0) to 0.11 (time 12-13 hours), to 0.13 (time 24-36 hours) and to (time 48-61 hours) with no overall significance. A highly significant correlation was found between Crs and a/A ratio (r = 0.698, P less than 0.001). We conclude that Exosurf does not induce immediate changes in oxygenation as does the instillation of (modified) natural surfactant preparations. However, after 12 and 24 hours of treatment oxygenation and Crs improve significantly.(ABSTRACT TRUNCATED AT 250 WORDS)

Multiple inert gas elimination technique by micropore membrane inlet mass spectrometry--a comparison with reference gas chromatography.

The mismatching of alveolar ventilation and perfusion (VA/Q) is the major determinant of impaired gas exchange. The gold standard for measuring VA/Q distributions is based on measurements of the elimination and retention of infused inert gases. Conventional multiple inert gas elimination technique (MIGET) uses gas chromatography (GC) to measure the inert gas partial pressures, which requires tonometry of blood samples with a gas that can then be injected into the chromatograph. The method is laborious and requires meticulous care. A new technique based on micropore membrane inlet mass spectrometry (MMIMS) facilitates the handling of blood and gas samples and provides nearly real-time analysis. In this study we compared MIGET by GC and MMIMS in 10 piglets: 1) 3 with healthy lungs; 2) 4 with oleic acid injury; and 3) 3 with isolated left lower lobe ventilation. The different protocols ensured a large range of normal and abnormal VA/Q distributions. Eight inert gases (SF6, krypton, ethane, cyclopropane, desflurane, enflurane, diethyl ether, and acetone) were infused; six of these gases were measured with MMIMS, and six were measured with GC. We found close agreement of retention and excretion of the gases and the constructed VA/Q distributions between GC and MMIMS, and predicted PaO2 from both methods compared well with measured PaO2. VA/Q by GC produced more widely dispersed modes than MMIMS, explained in part by differences in the algorithms used to calculate VA/Q distributions. In conclusion, MMIMS enables faster measurement of VA/Q, is less demanding than GC, and produces comparable results.

Performance of hydrophobic and hydrophilic silica membrane reactors for the water gas shift reaction

In this study, a novel molecular sieve silica (MSS) membrane packed bed reactor (PBR) using a Cu/ZnO/Al2O3 catalyst was applied to the low-temperature water gas shift reaction (WGS). Best permeation results were H-2 permeances of 1.5 x 10(-6) mol(.)s(-1) m(-2) Pa-1, H-2/CO2 selectivities of 8 and H-2/N-2 selectivities of 18. It was shown that an operation with a sweep gas flow of 80 cm 3 min(-1), a feed flow rate of 50 cm(3) min(-1) and a H2O/CO molar ratio of one at 280 degreesC reached a 99% CO conversion. This is well above the thermodynamic equilibrium and achievable PBR conversion. Hydrophilic membranes underwent pore widening during the reaction while hydrophobic membranes indicated no such behaviour and also showed increased H-2 permeation with temperature, a characteristic of activated transport. (C) 2003 Elsevier Science B.V. All rights reserved.

The structural characterization of carbon molecular sieve membrane (CMSM) via gas adsorption

The microstructure of a carbon molecular sieve membrane (CMSM) is characterized using adsorption equilibrium information. The pore size distributions of the CMSM derived from N-2 and CH4 adsorption isotherm are found to be consistent with each other and in agreement with the results of gas permeation experiments as well as the general characteristics of such molecular sieve materials. (C) 2003 Elsevier B.V. All rights reserved.

Silica membrane reactors for hydrogen production from water gas shift

This paper presents an analysis of membrane reactor (MR) operation and design for enhanced hydrogen production from the water gas shift (WGS) reaction. It has been established that membrane reactors can enhance an equilibrium limited reaction through product separation. However, the detailed effects of reactor setup, membrane configuration and catalyst volume have yet to be properly analysed for this reaction. This paper investigates new ideas for membrane reactors such as the development of new catalytic films, for improved interaction between the reaction and separation zones. Current membrane reactors utilise a packed bed of catalyst within the membrane tube, utilising a large volume of catalyst to drive reaction. This is still inefficient and provides only limited benefits over conventional WGS reactors. New reactor configurations look to optimise the interactive effects between reaction and separation to provide improved operation. In this paper, thin film catalysts were produced using dip coating and spray coating techniques. This technique produced catalyst coatings with good thickness, though the abrasion strength of the dip coated catalyst was quite low. The catalyst was tested in a packed bed reactor for temperature activity at low temperatures and catalyst activity at varying levels of excess water

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.

Morphology-properties relationship of gas plasma treated hydrophobic meso-porous membranes and their improved performance for desalination by membrane distillation

The impact on performance of the surface energy and roughness of membrane materials used for direct contact membrane distillation are critical but yet poorly investigated parameters. The capacity to alter the wettability of highly hydrophobic materials such as poly(tetra-fluoro-ethylene) (PTFE) by gas plasma treatments is reported in this paper. An equally important contribution from this investigation arises from illustrating how vaporized material from the treated sample participates after a short while in the composition of the plasma and fundamentally changes the result of surface chemistry processes. The water contact angle across the hydrophobic membranes is generally controlled by varying the plasma gas conditions, such as the plasma power, chamber pressure and irradiation duration. Changes to surface porosity and roughness of the bulk material as well as the surface chemistry, through specific and partial de-fluorination of the surface were detected and systematically studied by Fourier transform infra-red analysis and scanning electron microscopy. It was found that the rupture of fibrils, formed during membrane processing by thermal-stretching, led to the formation of a denser surface composed of nodules similar to these naturally acting as bridging points across the membrane material between fibrils. This structural change has a profound and impart a permanent effect on the permeation across the modified membranes, which was found to be enhanced by up to 10% for long plasma exposures while the selectivity of the membranes was found to remain unaffected by the treatment at a level higher than 99.99%. This is the first time that an investigation demonstrates how the permeation characteristics of these membranes is directly related to data from spectral, morphological and surface charge analyses, which provide new insights on the impact of plasma treatments on both, the surface charge and roughness, of PTFE porous materials.

A novel class of gas separation membrane based on organic ionic plastic crystals

The first use of organic ionic plastic crystals (OIPCs) as CO2 separation membranes is reported. The novel OIPC/PVDF nanofiber composites show CO2/N2 ideal selectivities of 30 at 35 °C. The dependence of gas permeability on the thermal phase of the plastic crystals is discussed.

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.

Evaluation of ion exchange as a pre-treatment option for coal seam gas water

The Coal Seam Gas (CSG) industry in Australia has grown significantly in recent years. During the gas extraction process, water is also recovered which is brackish in character. In order to facilitate beneficial reuse of the water, the CSG industry has primarily invested in Reverse Osmosis (RO) as the primary method for associated water desalination. However, the presence of alkaline earth ions in the water combined with the inherent alkalinity of the water may result in RO membrane scaling. Consequently, weak acid cation (WAC) synthetic ion exchange resins were investigated as a potential solution to this potential problem. It was shown that resins were indeed highly efficient at treating single and multi-component solutions of alkaline earth ions. The interaction of the ions with the resin was found to be considerably more complex that previously reported.

Strategies for the management and treatment of coal seam gas associated water

Coal seam gas (CSG) is a growing industry in Queensland and represents a potential major employer and deliverer of financial prosperity for years to come. CSG is a natural gas composed primarily of methane and is found trapped underground in coal beds. During the gas extraction process, significant volumes of associated water are also produced. This associated water could be a valuable resource, however, the associated water comprises of various salt constituents that make it problematic for beneficial use. Consequently, there is a need to implement various water treatment strategies to purify the associated water to comply with Queensland’s strict guidelines and to mitigate environmental risks. The resultant brine is also of importance as ultimately it also has to be dealt with in an economical manner. In some ways it can be considered that the CSG industry does not face a water problem, as this has inherent value to society, but rather has a “salt issue” to solve. This study analyzes the options involved in both the water treatment and salt recovery processes. A brief overview of the constituents present in Queensland CS water is made to illustrate the challenges involved and a range of treatment technologies discussed. Water treatment technologies examined include clarification (ballasted flocculation, dissolved air flotation, electrocoagulation), membrane filtration (ultrafiltration), ion exchange softening and desalination (ion exchange, reverse osmosis desalination and capacitance deionization). In terms of brine management we highlighted reinjection, brine concentration ponds, membrane techniques (membrane distillation, forward osmosis), thermal methods, electrodialysis, electrodialysis reversal, bipolar membrane electrodialysis, wind assisted intensive evaporation, membrane crystallization, eutectic freeze crystallization and vapor compression. As an entirety this investigation is designed to be an important tool in developing CS water treatment management strategies for effective management in Queensland and worldwide.

Forward osmosis as a pre-treatment for treating coal seam gas associated water: Flux and fouling behaviours

In this study, a bench scale forward osmosis (FO) process was operated using two commonly available FO membranes in different orientations in order to examine the removal of foulants in the coal seam gas (CSG) associated water, the water flux and fouling behaviours of the process were also investigated. After 48 h of fouling simulation experiment, the water flux declined by approximately 55 and 35% of its initial level in the TFC-PRO and CTA-PRO modes (support layer facing the feed), respectively, while the flux decline in the TFC-FO and CTA-FO modes (active layer facing the feed) was insignificant. The flux decline in PRO modes was caused by the compounding effects of internal concentration polarisation and membrane fouling. However, the declined flux was completely recovered to its initial level following the hydraulic cleaning using deionised water. Dissolved organic carbon (DOC), adenosine tri-phosphate (ATP) and major inorganic scalants (Ca, Mg and silica) in the CSG feed were effectively removed by using the FO process. The results of this study suggest that the FO process shows promising potential to be employed as an effective pre-treatment for membrane purification of CSG associated water.

Experimental Analysis of Water Vapor Diffusion Through Porous Membranes in a Proton Exchange Membrane Fuel Cell

We report the diffusion characteristics of water vapor through two different porous media, viz., membrane electrode assembly (MEA) and gas diffusion layer (GDL) in a nonoperational fuel cell. Tunable diode laser absorption spectroscopy (TDLAS) was employed for measuring water vapor concentration in the test channel. Effects of the membrane pore size and the inlet humidity on the water vapor transport are quantified through mass flux and diffusion coefficient. Water vapor transport rate is found to be higher for GDL than for MEA. The flexibility and wide range of application of TDLAS in a fuel cell setup is demonstrated through experiments with a stagnant flow field on the dry side.