Two stage abe fermentation with in situ pervaporation and high cell density

Dissertation presented to Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa for obtaining the master degree in Membrane Engineering

Pervaporation dehydration of isopropyl alcohol with NaY zeolite incorvorated hybrid membranes

With a solution technique, NaY zeolite incorporated, tetraethylorthosilicate-crosslinked poly(vinyl alcohol) membranes were prepared. The resulting membranes were tested for their ability to separate isopropyl alcohol/water mixtures by pervaporation in the temperature range of 30-50 degrees C. The effects of the zeolite content and feed composition on the pervaporation performance of the membranes were investigated. The experimental results demonstrated that both flux and selectivity increased simultaneously with increasing zeolite content in the membranes. This was explained on the basis of the enhancement of hydrophilicity, selective adsorption, and establishment of a molecular sieving action attributed to the creation of pores in the membrane matrix. The membrane containing 15 mass % zeolite exhibited the highest separation selectivity of 3991 with a flux of 5.39 X 10(-2) kg/m(2) h with 10 mass % water in the feed at 30 degrees C. The total flux and flux of water were close to each other for almost all the studied membranes, and this suggested that the membranes could be used effectively to break the azeotropic point of water/isopropyl alcohol mixtures to remove a small amount of water from isopropyl alcohol. From the temperature-dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water were significantly lower than those for isopropyl alcohol, and this suggested that the developed membranes had a higher separation efficiency for water/isopropyl alcohol systems. The activation energy values for total permeation and water permeation were found to be almost the same for all the membranes, and this signified that coupled transport was minimal because of the highly selective nature of the membranes. Positive heat of sorption values were observed in all the membranes, and this suggested that Henry's mode of sorption was predominant. (c) 2008 Wiley Periodicals, lnc.

Montmorillonite as a component of polysulfone nanocomposite membranes

Nanocomposite membranes containing polysulfone (PSI) and sodium montmorillonite from Wyoming (MMT) were prepared by a combination of solution dispersion and the immersion step of the wet-phase inversion method. The purpose was to study the MMT addition with contents of 0.5 and 3.0 mass% MMT in the preparation of nanocomposite membranes by means of morphology, thermal, mechanical and hydrophilic properties of nanocomposite membranes and to compare these properties to the pure PSf membrane ones. Small-angle X-ray diffraction patterns revealed the formation of intercalated clay mineral layers in the PSf matrix and TEM images also presented an exfoliated structure. A good dispersion of the clay mineral particles was detected by SEM images. Tensile tests showed that both elongation at break and tensile strength of the nanocomposites were improved in comparison to the pristine PSf. The thermal stability of the nanocomposite membranes, evaluated by onset and final temperatures of degradation, was also enhanced. The hydrophilicity of the nanocomposite membranes, determined by water contact angle measurements, was higher; therefore, the MMT addition was useful to produce more hydrophilic membranes. (C) 2009 Elsevier B.V. All rights reserved.

High selectivity microporous silica membranes for lactic acid dehydration

Lactic acid (LA) has significant market potential for many industries including food, cosmetics, pharmaceuticals, medical and biodegradable materials. Production of LA usually begins with the fermentation of glucose but subsequent stages for the enrichment of lactic acid are complex and energy intensive and could be minimised using water selective membrane technology. In this work, we trialled a highly selective hydrostable carbonised template molecular sieve silica (CTMSS) membrane for the dehydration of a 15 vol% aqueous lactic acid solution with 0.1 vol% glucose. CTMSS membrane films were developed by dip-coating ceramic substrates with silica sols made using the acid catalysed sol-gel process. Permeation was performed by feeding LA/glucose solution to the membrane cell at 18°C in a standard pervaporation setup. The membrane showed selective transport of water from the aqueous feed to the permeate while glucose was not detected. CTMSS membrane permeate flux stabilised at 0.2 kg.m-2.hr-1 in 3.9 hours, and reduced LA to lower than 0.2 vol%. Flux through the CTMSS micropores was activated, displaying increased initial flux to 1.58 kg.m-2.hr-1 at 60°C. To enrich a 1 l.min-1 stream to 85% LA in a single stage, a minimum membrane area of 324 m2 would be required at 18°C. Increased operating temperature to 80°C significantly reduced this area to 24 m2 but LA levels in the permeate stream increased to 0.5 vol%. The highly selective CTMSS membrane technology is an ideal candidate for LA purification. CTMSS membrane systems operate stably in aqueous systems leading to potential cost reductions in LA processing for future markets.

Caution on the storage of waters and aqueous solutions in plastic containers for hydrogen and oxygen stable isotope analysis

RATIONALE The choice of containers for storage of aqueous samples between their collection, transport and water hydrogen (2H) and oxygen (18O) stable isotope analysis is a topic of concern for a wide range of fields in environmental, geological, biomedical, food, and forensic sciences. The transport and separation of water molecules during water vapor or liquid uptake by sorption or solution and the diffusive transport of water molecules through organic polymer material by permeation or pervaporation may entail an isotopic fractionation. An experiment was conducted to evaluate the extent of such fractionation. METHODS Sixteen bottle-like containers of eleven different organic polymers, including low and high density polyethylene (LDPE and HDPE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), and perfluoroalkoxy-Teflon (PFA), of different wall thickness and size were completely filled with the same mineral water and stored for 659?days under the same conditions of temperature and humidity. Particular care was exercised to keep the bottles tightly closed and prevent loss of water vapor through the seals. RESULTS Changes of up to +5 parts per thousand for d2H values and +2.0 parts per thousand for d18O values were measured for water after more than 1?year of storage within a plastic container, with the magnitude of change depending mainly on the type of organic polymer, wall thickness, and container size. The most important variations were measured for the PET and PC bottles. Waters stored in glass bottles with Polyseal (TM) cone-lined PP screw caps and thick-walled HDPE or PFA containers with linerless screw caps having an integrally molded inner sealing ring preserved their original d2H and d18O values. The carbon, hydrogen, and oxygen stable isotope compositions of the organic polymeric materials were also determined. CONCLUSIONS The results of this study clearly show that for precise and accurate measurements of the water stable isotope composition in aqueous solutions, rigorous sampling and storage procedures are needed both for laboratory standards and for unknown samples. Copyright (c) 2012 John Wiley & Sons, Ltd.

Pervaporação: uma técnica de separação contínua não-cromatográfica

A brief discussion of the non-chromatographic continuous separation techniques is presented emphasizing the pervaporation process. It makes interesting choices for implementing various preliminary operations of the analytical process in order to accommodate the raw sample to the measuring instrument. Discussions include the perceived advantages and disadvantages, the underlying principles of pervaporation process, the flexible module and fields of application.

Determinação em fluxo do carbonatoresidual do solo empregando pervaporação

The objective of this study was to develop a method for the direct determination of residual CO3(2-) in acid soil using a flow system coupled with pervaporation. The gas released from the acidified sample was separated though a hydrophobic membrane and detected by conductivimetry. The detection limit was 0.054 mmol c kg-1 for CO2/CO3(2-) with relative error of 3.1%. The analytical frequency was 20 samples per hour. The method is recommended for studying the reactions and kinetics of lime applied in acid soils.

Membraanien kestävyys ionisessa nesteessä

Tämän diplomityön tavoitteena oli etsiä mahdollisimman hyvin ionista nestettä kestävä yleisesti kaupallisesti saatavilla oleva nano- tai ultrasuodatusmembraani. Kirjallisuusosassa on perehdytty yleisesti membraanitekniikan ja ionisten nesteiden historiaan sekä niiden ominaisuuksiin ja käyttösovelluksiin. Membraaniprosesseista on lyhyesti käyty läpi mikro-, ultra- ja nanosuodatus sekä käänteisosmoosi ja pervaporaatio. Kokeellisessa osassa tutkittiin neljäntoista kaupallisesti saatavilla olevien nano- ja ultrasuodatusmembraanien kestävyyttä ionisessa nesteessä. Tutkimuksessa käytettyjen membraanien vesi- ja malliaineliuosvuon arvoja sekä retentioita vertailtiin ennen ja jälkeen ioniselle nesteelle altistusta. Tulokset osoittivat, että polyamidista, polyeetterisulfonista ja sulfonoidusta polyeetterisulfonista valmistettujen membraanien suodatusominaisuudet muuttuivat niiden altistuessa ioniselle nesteelle. Näiden membraanien permeabiliteetit ja retentiot laskivat viikon altistuksen jälkeen merkittävästi. Erityisesti liuottimia kestäviksi suunnitellut membraanit säilyttivät erotusominaisuutensa paremmin.

Biomassahydrolysaattien puhdistus uutolla

Lignoselluloosasta koostuvasta biomassasta valmistetaan hydrolysoimalla sokereita, jotka jatkojalostetaan fermentoimalla bioetanoliksi. Bioetanolia käytetään fossiilisten polttoaineiden korvaajana esimerkiksi ajoneuvoissa. Bioetanolin valmistuksessa pyritään mahdollisimman hyvään saantoon, jotta sen valmistus olisi taloudellisesti kannattavaa. Hydrolyysin aikana syntyy sokerien lisäksi orgaanisia happoja, furaanin johdannaisia sekä fenolisia yhdisteitä. Yleisimpiä syntyviä yhdisteitä ovat muun muassa etikkahappo, furfuraali ja hydroksimetyylifurfuraali. Nämä yhdisteet haittaavat sokerien fermentointiprosessia ja pienentävät etanolin saantoa. Fermentointiprosessia haittaavien yhdisteiden poistoon hydrolysaattiliuoksesta voidaan käyttää esimerkiksi haihdutusta, membraanierotusta, adsorptiota, saostusta, sekä uuttoa. Tämän työn tarkoituksena oli tutkia leikkaussekoittimen soveltuvuutta biomassahydrolysaatin epäpuhtauksien erotukseen. Lisäksi kirjallisuusosassa on esitetty hydrolysointiprosessissa syntyviä haitta-aineita ja niiden erotusmenetelmiä.

Aroma volatiles recovered in the water phase of cashew apple (Anacardium occidentale L.) juice during concentration

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sodium Alginate-Based Ionic Conducting Membranes

The present study investigates gel polymer electrolytes (GPEs) based on sodium alginate plasticized with glycerol containing either CH3COOH or LiClO4. The membranes showed ionic conductivity results of 3.1 x 10(-4) S/cm for the samples with LiClO4 and 8.7x10(-5) S/cm for the samples with CH3COOH at room temperature. The samples also showed thermal stability up to 160 degrees C, transparency of up to 90%, surface uniformity and adhesion to glass and steel. Moreover, Dynamic Mechanical Analysis revealed two relaxations for both samples and the Ea values were between 18 and 36 kJ/mol. All the results obtained indicate that alginate-based GPEs can be used as electrolytes in electrochemical devices.

Processi integrati per l’intensificazione di processo: reazione di fotocatalisi accoppiata alla pervaporazione, la dialisi e all’ozonizzazione

L’accoppiamento di diverse operazioni unitarie può in certi casi portare ad una cosiddetta “intensificazione di processo”, cioè ad un aumento sostanziale delle rese, dell’efficienza e della sostenibilità. Nel presente lavoro sono state pertanto analizzate le potenzialità di accoppiamento della fotocatalisi, il più studiato tra i “processi di ossidazione avanzata”, sia con alcuni processi a membrana per la sintesi verde di aromi sia con l’ozonizzazione per la depurazione di acque. È stato dimostrato che in entrambi i casi l’ottenimento di una significativa intensificazione di processo dipende in gran parte dai parametri operativi, in particolare dal rapporto, delta, tra la velocità caratteristica di fotocatalisi e quella del processo accoppiato. Nel caso della sintesi di aromi, in cui la fotocatalisi viene accoppiata con la pervaporazione o con la dialisi ricircolando al reattore il retentato dalla cella con la membrana. Il parametro delta dipende dalla velocità di reazione, dalle proprietà di trasporto delle membrane e naturalmente dal volume del rettore e dall’area della membrana. La reazione fotocatalitica produce l’aroma, ad esempio vanillina da acido ferulico, per ossidazione parziale e grazie al recupero del prodotto se ne evita l’ulteriore ossidazione aumentandone pertanto la resa. L’operare in apparati separati offre diversi vantaggi come la possibilità di variare senza vincoli il rapporto tra area della membrana e volume del reattore, ma impone di considerare anche il grado effettivo di accoppiamento dei processi. In questo caso, come evidenziato dal modello matematico, un sufficientemente elevato rapporto di ricircolo consente comunque di integrare efficacemente i processi. Nell’ozonizzazione fotocatalitica si hanno due importanti vantaggi: l’aumento della velocità di degradazione grazie alla sinergia tra i processi e la capacità di controllare la formazione di prodotti pericolosi. La sinergia viene massimizzata ad un valore ottimale di delta, mentre la formazione dei prodotti indesiderati viene controllata operando secondo le procedure che sono state individuate.