This study was to investigate theory and application of Osmotic Distillation (OD). OD is a new novel membrane separation process used for the concentration of aqueous solutions such as fruit juices without the application of heat. The present work was undertaken to investigate flux limitations focusing on feedside, membrane and stripper side characteristics of OD. Once the limiting areas were identified, further studies were undertaken to determine methods of minimizing those limitations without losing the quality and integrity of the liquid feed. A laboratory scale OD system was used to simulate the industrial process which takes place during the production of grape juice concentrate for the fruit juice industry. Results of a UF pretreatment study showed that the use of UF membranes with pore diameters of 0.1 fÝm or less as a pretreatment for the subsequent OD of grape juice resulted in significant increases in OD flux over that observed for juice not subjected to UF. The study of the physical properties of the feed played an important role in the explanation of the OD process. The increase in OD flux was attributed to a reduction in juice viscosity as the result of the removal of protein and other high molecular weight components. Apart from an increase in OD flux, UF pretreatment of the grape juice proved to be beneficial in other areas of the OD process. HPLC measurements showed that the normal concentration of fermentable sugars in standard 68 oBrix concentrate can be achieved at a lower Brix value in feed subjected to UF pretreatment, further reducing the need to handle highly viscous feeds. UF pretreatment also resulted in an increase in juice surface tension consequently reducing the tendency for membrane wet-out to occur. The study of the deoxygenation of the feed solution shows that the removal of dissolved gases by the pre boiling method and the perstraction with chemical reaction (PCR) method both had a positive affect on OD flux. Pre boiling the brine resulted in an indirect reduction in dissolved oxygen in the feed. Pre boiling both the feed and brine, further increased the flux. Throughout the PCR study, it was evident that stripper side mass transfer of O2 was not limited by flowrate but was limited by higher stripper concentration. However, the latter had an insignificant effect when the sulfite-oxygen reaction was catalysed. The use of a catalyst and increase in temperature gave a significant improvement in overall mass transfer coefficient. Ten types of hydrophobic microporous membranes were tested for their influence on OD flux. While the pore diameter is a considerable factor in mass transport of gases through the membrane, it was also noted that the type of membrane material used had an affect on the overall mass transfer. All top three performing membranes had pore diameters of 0.2 x 10-6 m and were made from polytetrafluoroethylene (PTFE). The choice of brine to use as the stripper was based on criteria that were confirmed by the brine studies performed here. The best performing stripper solutions demonstrating the greatest improvement in OD flux over the most commonly used brines, NaCl, CaCl2 and CH3COOK were aqueous solutions of potassium salts of phosphoric acid, pyrophosphoric acid and blends thereof. These salts agreed with all the required characteristics of a suitable brine, demonstrating high solubility rates, supporting the ability to lower water vapour pressure. The study of the corrosion effects of brine salts confirmed the phosphate salts are superior demonstrating some of the lowest corrosion rates and highest pH.

The present work was undertaken to develop a composite osmotic distillation (OD) membrane consisting of a thin hydrogel coating on a microporous hydrophobic substrate for the concentration of aqueous feeds containing surface-active agents. The range of OD applications using the hydrophobic membrane alone have been severely limited by the propensity for membrane wet-out when contacted by amphiphilic agents such as oils, fats and detergents. Wet-out allows the feed solution to track freely through the membrane pores with a resulting loss of solutes and a decrease in selectivity. The rationale for the approach taken was based on the hypothesis that the high water selectivity of the hydrophilic coating would maintain good water mass transfer to the underlying hydrophobic substrate but exclude other components including surface-active agents. The first stage of this work involved the identification of potential coating materials and the fabrication and structural characterization of films of these materials to determine their suitability. The second stage involved the development of techniques to facilitate adhesion of the hydrophilic coatings to the hydrophobic substrate, and the testing of the resulting composite membranes for OD performance and resistance to wet-out by surface-active agents. Sodium alginate was selected as the major coating component on the basis of its non-toxicity and its potential for stable hydrogel formation. Structural characterization of noncrosslinked films and films crosslinked using a water-soluble carbodiimide (WSC) was carried out using differential scanning calorimetry (DSC), Fourier Transform infrared spectroscopy (FT-IR) and swelling measurements. Maximum crosslinking through esterification of hydroxyl and carboxylic acid groups on adjacent polymer strands using the film immersion method was achieved with a non-solvent (ethanol) concentration of 60 vol % and a WSC concentration of 100 mM at pH 4. These conditions resulted in a hydrogel with an equilibrium water content of 60 wt %. DSC measurements of noncrosslinked and crosslinked alginate films showed an increase in crystallinity and hence rigidity on crosslinking. Therefore, several coatings were prepared as blends of sodium alginate and amorphous highly flexible carrageenan gum in order to meet the flexibility requirements of a membrane subjected to varying operating pressures in an industrial OD plant. Structural characterization with respect to polymer blend ratio was carried out using scanning electron microscopy (SEM), DSC, X-ray diffraction (XRD). The optimisation for crosslinking conditions was undertaken as for sodium alginate alone. Optimum conditions for film preparation were 20 wt % carrageenan content and a crosslinking medium containing 60 vol % non-solvent (ethanol) and 120 mM WSC at pH 4. These conditions produced a hydrogel with an equilibrium water content of 85 wt %. Two different techniques were employed to anchor the coatings on substrate PTFE membranes. For membranes with a nominal diameter of 0.2 µm, the technique involved surface tension adjustment of the coating solution by ethanol addition in order to enhance penetration of the coating solution meniscus into the substrate pores. This was followed by polymer precipitation by the selective removal of water using OD to provide structural interlocking. T-peel strength measurements showed that this technique resulted in a ten-fold increase in adhesion strength when compared with a coating cast without surface tension adjustments. For membranes with a nominal diameter of 0.1µm, an interfacial bonding agent, myristyltrimethylammonium bromide (MTMA), was used. This technique gave a three-fold increase in adhesion strength relative to that of coating cast without the use of MTMA. The composite membranes were tested in extended OD trials using pure water and feeds containing limonene, the major surface-active components of orange oil. The sodium alginate-carrageenan blend membrane, which was the preferred membrane based on flexibility and water sorption considerations, was also tested against full-cream milk and an industrial detergent, sodium dodecylbenzene sulfonate (DBS). The results indicated that the coatings offered little resistance to water transport and were effective in providing protection against membrane wet-out. Durability trials showed that the composite membranes retained their integrity in water for a minimum of 30 days. Overall, this study has expanded the potential applications of OD to include many important industrial concentration steps that are currently being undertaken by conventional processes with unsatisfactory results. These include the concentration of citrus juices, full-cream milk and nuclear power plant liquid waste. These feeds contain limonene, fats and detergents respectively, all of which wet out unprotected hydrophobic membranes.

La presente tesis estudia el desarrollo de tecnologías de separación y recuperación de aromas. Se busca obtener dos clases distintas de productos, concentrados aromáticos y bebidas parcialmente desalcoholizadas. En ambos productos se requiere una alta calidad aromática.Distintos casos de estudio se han seleccionado:i) La separación concentración del 2,4-decadienoato de etilo, aroma impacto de la pera, y ii) la separación-concentración del trans-2-hexen-1-ol, aroma impacto de los arándanos. En ambos casos, se tratan corrientes acuosas de la etapa de concentración de zumos en la indsutria. Para el estudio de la separación /concentración del aroma de pera se aplica adsorción en Carbón Activo Granular y Destilación con Membranas a Vacío, y para el aroma del arándano se selecciona la Pervaporación. Para todos estos casos se analiza el rendimiento del proceso y se desarrolla el modelo matemático obteniéndose sus principales parámetros de transporte.iii) La reducción del contenido de etanol en vino mediante Destilación Osmótica. Se ha desarrollado el modelo matemático que describe el transporte del etanol y los compuestos aromáticos. La validación del modelo y el análisis sensorial se llevaron a cabo mediante vino real. / The thesis document deals with the development of technologies for the separation and recovery of aromatic compounds. Two different kind of products are sought, aroma concentrates from fruit juices and partially de-alcoholised beverages. On both products high aromatic quality is required.Several cases of study have been selected: i) The separation of separation-concentration of ethyl E-2, Z-4-decadienoato, pear impact aroma compound, and ii) separation-concentration of E-2-hexen-1-ol, bilberries impact aroma compound. In both cases, aqueous streams to be treated in the industry would come from the juice concentration stage. The study of the separation and concentration of the pear aroma compound was made by using Adsorption onto Granular Activated Carbon and Vacuum Membrane Distillation, and for the bilberry aroma compound, Pervaporation was selected. For all of these cases of study, the performance analysis and mathematical modeling have been performed and the main transport parameters.iii) The reduction of the alcohol content of wine by Osmotic Distillation. A mathematical model describing both the ethanol and aroma compounds transport was developed. Model validation and sensorial analysis on real wine were made.