D.Phil. (Chemistry) / Please refer to full text to view abstract

Orientador: Miriam Dupas Hubinger / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-27T10:07:35Z (GMT). No. of bitstreams: 1 Rabelo_RenataSantos_M.pdf: 54735801 bytes, checksum: 79deeea44988fbcfd818411f5b804573 (MD5) Previous issue date: 2015 / Resumo: A alcachofra (*Cynara scolymus L.*) é uma herbácea perene pertencente à família *Asteraceae. *A espécie, rica em compostos fenólicos, é originária de regiões subtropicais, mas também é cultivada no Brasil, onde maior parte da produção se concentra no interior paulista e é voltada à indústria de conservas*,* que geralmente descarta como resíduo, brácteas externas e internas da planta. Em vista disso, o presente trabalho teve como objetivo, desenvolver extratos ricos em compostos bioativos, principalmente fenólicos, a partir dos resíduos de alcachofra, por meio do estudo do processo de extração assistida por ultrassom e da avaliação do desempenho do processo de concentração por membranas. Inicialmente, foram estudadas as variáveis da extração hidroalcoólica assistida por ultrassom como potência do ultrassom, composição do solvente e razão sólido/solvente. Após esta etapa, dois dos extratos, nas melhores condições de extração, foram concentrados por nanofiltração, usando três membranas de poliamida (NF270, DK e DL), em um sistema de filtração tangencial operado a 20 bar. Os processos foram avaliados quanto ao rendimento de compostos fenólicos (Folin-Ciocauteau), ácido clorogênico (CLAE-DAD) e capacidade antioxidante (DPPH e FRAP). Os rendimentos obtidos com a integração das etapas de extração e concentração, a partir de um fator de redução de volume de 2,5 foram de 559,59 ± 32,09 mg de ácido gálico equivalente/g de extrato seco para fenólicos totais, e 22,95 ± 0,35 mg de ácido clorogênico/g de extrato seco, para ácido clorogênico. Os resultados para capacidade antioxidante foram de 198,88 ± 15,15 mg Trolox equivalente/g de extrato seco, para o método de DPPH, e de 385,70 ± 0,35 mg Trolox equivalente/g de extrato seco para o método FRAP. O declínio do fluxo de permeado no processo de nanofiltração foi causado pela formação de torta, e a membrana que apresentou menor resistência ao fluxo, maior estabilidade ao longo do processo de filtração e maior retenção dos compostos de interesse, foi a DK, sendo esta a mais indicada para concentração dos extratos avaliados nesse trabalho / Abstract: The artichoke (Cynara scolymus L.) is a perennial herb belonging to the family Asteraceae. The species, rich in phenolic compounds, is originally from subtropical regions, but is also cultivated in Brazil, where most of its production is concentrated in the interior of São Paulo, and is geared to the canning industry, where external and internal bracts of plant are usually discarded as waste. The present study aimed to develop extracts rich in bioactive compounds, mainly phenolics, from artichoke waste by the study of the extraction process assisted by ultrasound and the assessment of the performance of the membrane concentration process. Initially, the variables of water-alcohol extraction assisted by ultrasound (ultrasound power, solvent composition and solid/solvent ratio) were studied, after this, two extracts in the best extraction conditions were concentrated by nanofiltration, using three polyamide membranes (NF270, DK, DL), in a tangential filtration system operated at 20 bar. Process yields were evaluated for phenolic compounds (Folin-Ciocauteau), chlorogenic acid (HPLC-DAD) and antioxidant capacity (DPPH and FRAP). The yield obtained with the integration of extraction and concentration processes, from a volume reduction factor of 2.5 were of 559.59 ± 32.09 mg of gallic acid equivalent/g dry extract for total phenolics, and 22.95 ± 0,35 mg of chlorogenic acid/g of dry extract, for chlorogenic acid. The results for antioxidant capacity were of 198.88 ± 15.15 mg Trolox equivalent/g of dry extract to the DPPH method, and 385.70 ± 0.35 mg Trolox equivalent/g of dry extract for the FRAP method. The decline of the permeate flux in nanofiltration process is due to cake formation. The membrane that showed less resistance to flow, greater stability over the filtration process and more retention of the compounds of interest was DK, which is the most suitable for concentration of the extract evaluated in this work / Mestrado / Engenharia de Alimentos / Mestra em Engenharia de Alimentos

Nanofiltration and seawater reverse osmosis desalination are still considered energy-intensive processes. Seawater desalination can be 25 times more energy-intensive compared to conventional water treatment processes. Biofouling is a significant problem in achieving sustainable desalination, as it increases the energy demands and the overall water cost. Limiting the biodegradable substrate concentration in the feed water is proposed as a suitable approach to control biofouling in desalination membranes. Until now, nutrient manipulation studies have not fully elucidated to which extent this technique affects biofilm morphology and if the manipulated biofilms are easier to control and remove with a chemical-free approach. The main objective of this Ph.D. study is to provide a comprehensive assessment of the effect of nutrient manipulation on the physical properties of the developed biofilm to decrease the impact of biofouling on system performance and enhance the cleanability of biofilms in membrane systems. The aspects of the study included biofilm development and related system performance under varying feed water biodegradable carbon and phosphorous concentrations and the impact of permeation. The results of this study indicate that lowering the assimilable organic carbon and phosphorus concentration in the feed water controls biofilm formation and prolongs membrane system performance. A strategy of enhancing the hydraulic cleanability of biofilms in RO systems could involve avoiding the increase of the phosphorus concentration by eliminating the use of phosphonate-based antiscalants. The higher detachment for biofilms grown at a lower phosphorus concentration was explained by more soluble polymers in the EPS, resulting in a lower biofilm cohesive and adhesive strength. We demonstrated that the phosphorus concentration in the feed water affected the microbial and EPS composition. A homogenous bacterial community composition was found over the biofilm height. Permeation played a role in shaping biofilm localization, and therefore, the observed impact on the system performance parameters. This Ph.D. dissertation represents an exciting advance towards greener desalination by controlling and enhancing the cleanability of biofilms through feed water nutrient manipulation.

Membrane processes are considered energy-efficient for water desalination and treatment. However most membranes are based on polymers prepared from fossil petrochemical sources. The development of multilayer membranes for nanofiltration and ultrafiltration, with thin selective layers of naturally available cellulose, has been hampered by the availability of non-aggressive solvents. We propose the manufacture of cellulose membranes based on two approaches: (i) silylation, coating from solutions in tetrahydrofuran, followed by solvent evaporation and cellulose regeneration by acid treatment; (ii) casting from solution in 1-ethyl-3-methylimidazolum acetate ([C2mim]OAc), an ionic liquid, followed by phase inversion in water. In the search for less harsh, greener membrane manufacture, the combination of cellulose and ionic liquid is of high interest. Due to the abundance of OH groups and hydrophilicity, cellulose-based membranes have high permeability and low fouling tendency. Membrane fouling is one of the biggest challenges in membrane industry and technology. Accumulation and deposition of foulants onto the surface reduce membrane efficiency and requires harsh chemical cleaning, therefore increasing the cost of maintenance and replacement. In this work the resistance of cellulose 5 membranes towards model organic foulants such as Suwanee River Humic Acid (SRHA) and crude oil have been investigated. Cellulose membrane was tested in this work for oil-water (o/w) separation and exhibited practically 100 % oil rejection with good flux recovery ratio and membrane resistivity. The influence of anionic, cationic and ionic surfactant as well as pH and crude oil concentration on oil separation was investigated, giving a valuable insight in experimental and operational planning.

In the last decades, there has been a trend towards bio-inspired approaches for the formation of nanocoatings as well as to accomplish energy-intensive industrial separations in a more sustainable fashion. Solvent Resistant Nanofiltration (SRNF) is a pressure driven technology where the operation conditions are moderate and additional waste streams are minimized, making this a favorable energy efficient approach for challenging molecular separations such as purification of active pharmaceutical ingredients, production of specialty chemicals and in the petrochemical industry just to mention a few examples, where this technology can be currently applied. The overall performance of SRNF membranes is determined by solute/solvent interactions with the membrane top layer. Therefore, the modification of the membrane surface becomes crucial to obtain high-performance SRNF membranes, as well as exploring novel and green approaches to improve the separation properties of SRNF membranes, without sacrificing their permeation properties. One alternative for the fabrication of the thin-films in SRNF membranes proposed in this work is the use of biopolyphenolic molecules. Among the many classes of phenolic biomolecules, plant phenols are capable of binding and cross-linking due to their strong interfacial activity. Here, the successful optimization of the interfacial polymerization reaction for the manufacture of SRNF membranes is demonstrated by replacing the common toxic amines used for this method with natural occurring bio-polyphenols such as dopamine, tannic acid, morin hydrate and catechin. These bio-polyphenols can be found in mussels, date fruits, guava fruits and green tea respectively and they were used to form a selective thin film on top of a crosslinked polyacrylonitrile or a cellulose support. These membranes have shown an exceptional performance and resistance towards harsh solvent environments. Due to the incorporation of natural compounds for the manufacture, they provide a cost-effective alternative for industrial separations due to the ease of chemical modification and preparation, which is potentially easy to scale up at low cost taking advantage of the natural compounds for their manufacture.

Abstract: The worldwide consumption of pharmaceuticals and personal care products for healthcare purposes has resulted in the occurrence of organic micropollutants (OMPs) in freshwater and wastewater resources. These pollutants are not entirely removed by conventional water and wastewater treatment plants, leading to potential human and animal health problems. Membranes are a promising technology capable of solving this problem. This study evaluated the ability of high-pressure driven membranes such as nanofiltration (NF) and reverse osmosis (RO) to remove OMPs. A total of 13 compounds were selected so that a broad range of molecular weights and octanol-water partition coefficients (log Kow) could be studied. Three commercial thin-film-composite polyamide membranes (NF1, NF6, and RO4) were tested. Filtration experiments were conducted using a cross-flow membrane system at pH 6 8 and 10. The membranes were characterized by atomic force microscopy and scanning electron microscopy that allowed a more profound understanding of the membrane surface structures. Experimental results showed that the permeate flux of NF6 is dependent on the pH of the feed solution. An increase in the feed pH from 6 to 10 resulted in an increase on the permeate flux from 14.5 to 24 L m-2 h-1 bar-1, which caused a drop in the rejection of some OMPs by NF6. Nevertheless, for most OMPs, as pH increased to 10, rejection increased for NF1 and RO4 due to electrostatic repulsion between the negatively charged membrane surface and the ionized OMPs. It was observed that ionic hydrophobic compounds could be highly rejected (> 95%) by NF1 and RO4. The study indicated that the rejection of non-ionic hydrophilic and hydrophobic OMPs were rejected effectively by RO4 (> 90%), and the rejection was mostly dominated by size exclusion and hydrophobic interactions between the membrane and the OMPs. Furthermore, the study revealed that the properties of the compounds, the intrinsic properties of the membrane, and the operating conditions have a significant influence on the rejection of OMPs.

Owing to the maldistribution of precipitation in the harsh climatic region has resulted in the deficit between freshwater demand and natural supply or water scarcity in these countries. Seawater desalination has emerged as one of the most reliable methods to bridge this gap. However, the thermal desalination (MED and MSF) process faces challenges related to surface scaling phenomena, such as temperature and seawater concentration. Innovative thermodynamic processes and technologies have the potential to overcome these limitations. On one hand, the top brine temperature (TBT) limit can be raised by partially removing the multivalent ions such as SO42-, Mg2+, Ca2+, Cl-, and Na+ dissolved in the seawater. One of the main drawbacks of the current MED processes is their vulnerability to scaling at temperatures above 70°C.. This limitation deprives the technology to be energy efficient and reduces its optimal productivity. However, by implementing an optimized pre-treatment of seawater feed using NF membranes, the efficiency of the process can be significantly improved. In the pilot plant, the experiment was conducted to investigate the efficacy of NF (nanofiltration) as a physical pre-treatment method for partially removing undesirable ions of dissolved salts in Red Sea water, thereby mitigating scaling issues beyond the upper TBT limit in thermal desalination systems. Utilizing the NF-270 membrane, the optimal operating feed pressure of 15 bar was determined to ensure effective ion removal while minimizing operational expenditures (OpEx). The results demonstrated high removal rates, with 97% removal of Sulfate (SO42-), 73% removal of Magnesium (Mg2+), 49% removal of Calcium (Ca2+), 17% removal of Sodium (Na+), and 16% removal of Chloride (Cl-). By employing NF as a pre-treatment method, the concentrations of these ions were significantly reduced, allowing for thermal desalination plants to operate at higher temperatures, with a maximum TBT of 120°C. This, in turn, has the potential to substantially increase water production yield in thermally driven plants by incorporating a greater number of stages in a green new design plant or by exploiting larger temperature differences in existing plants.

Organic solvent nanofiltration (OSN) is a membrane-based sustainable alternative to conventional separation techniques because it is non-thermal and energy-efficient. The fabrication of membranes usually includes fossil-based polymers and toxic solvents that present significant challenges. For example, its declining availability, concerns about its degradability and cross-contamination that involve toxicity risks. Nowadays, there is an increasing interest in the development of more sustainable membranes that maintain an optimum performance even in harsh solvents. The aim of my thesis research is to develop stable OSN membranes from cellulose acetate and explore the use of deacetylation reactions. The effect of the degree of acetylation on the membrane performance and stability in different organic solvents was investigated. The chemical composition and morphology were investigated using Fourier Transform Infrared (FTIR), Scanning Electron Microscope (SEM), and Atomic Force Microscopy (AFM). It was found that cellulose acetate membranes with less than 22% acetylation present a satisfactory solvent resistance and rejection in harsh solvents, such as DMF and acetone. In the performance tests were identified two main trends: one for polar protic solvents and one for polar aprotic solvents. This was attributed to their capacity to interact with the membrane via H-bond formation. The molecular weight cutoff (MWCO) was in the range of 735–325 g mol–1 in aprotic solvents and higher than 885 g mol–1 for polar protic solvents. The results found in this research can be translated into a reduce in costs, waste generated, energy required, and time employed in the fabrication of membranes. Also, it opens potential areas in the industry as it can be implemented in harsh solvent environments.

Organic solvent nanofiltration (OSN) is a low-energy alternative for continuous separations in the chemical industry. As the pharmaceutical sector increasingly turns toward continuous manufacturing, OSN could become a sustainable solution for chiral separations. Here we present the first comprehensive theoretical assessment of enantioselective OSN processes. Lumped dynamic models were developed for various system configurations, including structurally diverse nanofiltration cascades and single-stage separations with side-stream recycling and in situ racemization. Enantiomer excess and recovery characteristics of the different processes were assessed in terms of the solute rejection values of the enantiomer pairs. The general feasibility of stereochemical resolution using OSN processes is discussed in detail. Fundamental connections between rejection selectivity, permeance selectivity, and enantiomer excess limitations are revealed. Quantitative process performance examples are presented based on theoretical rejection scenarios and cases from the literature on chiral membranes. A model-based prediction tool can be found on www.osndatabase.com to aid researchers in connecting materials development results with early-stage process performance assessments.

L’utilisation de l’ultrafiltration (UF) pour la concentration du lait de fromagerie est une pratique courante en industrie laitière. Dépendamment de l’usage de ce type de concentré, plusieurs avantages y ont été associé, tels que des gains de rendements et de productivité. D’autres procédés baromembranaires, tels que l’osmose inverse (RO) et la nanofiltration (NF), actuellement utilisés pour la gestion des effluents de l’industrie laitière, semblent prometteurs pour réaliser cette étape de concentration du lait de fromagerie. En effet, les gains de rendements attendus avec ces deux procédés sont plus élevés qu’avec l’ultrafiltration car tous les composés du lait sont concentrés et peuvent potentiellement être retenus dans le fromage. De plus, le perméat généré ne contient essentiellement que de l’eau et peut être réutilisé au sein de l’usine. Cependant, ces types de concentrés laitiers (NF et RO) ne sont que peu connus et leur utilisation en fromagerie ne peut être envisagée actuellement. Le but de ce projet était donc de caractériser les concentrés laitiers provenant de l’osmose inverse ou de la nanofiltration du lait et de comprendre les facteurs influençant leurs propriétés fromagères. Une première étude a permis de mettre en évidence l’impact des procédés de concentration du lait sur les propriétés physico-chimiques des concentrés. Il a été montré que les équilibres entre les phases soluble et colloïdale n’étaient pas impactés de façon notable par la concentration du lait, que ce soit par UF, NF ou RO. Ces deux derniers procédés ont, en revanche, mené à une diminution du pH et une augmentation de la force ionique et de la viscosité des concentrés. A pH constant et teneur en protéines similaires, les propriétés de coagulation par la présure ont été impactées par le type de concentrés utilisé et globalement un concentré UF avait de meilleures propriétés de coagulation qu’un concentré NF ou RO. Ces différences ont été attribuées à la force ionique élevée et/ou à la viscosité élevée. Cette première partie a donc permis de déterminer l’impact du procédé de concentration sur les caractéristiques des concentrés et de mettre en évidence les différences de propriétés entre plusieurs types de concentrés laitiers. Dans une seconde étude, l’impact du type de concentré et de l’ajustement de pH sur les propriétés de coagulation par la présure a été déterminé. Les résultats obtenus dans la première partie du projet ont montré des différences de temps de coagulation des concentrés UF et RO. Pour mieux comprendre quel paramètre était responsable, les cinétiques d’hydrolyse de la caséine κ par la présure ont été étudiées. Deux résultats majeurs ont pu être mis en évidence. Premièrement, de faibles variations de pH ont permis d’obtenir des cinétiques de coagulation par la présure similaires entre un concentré RO et un concentré UF, malgré les différences importantes de composition. Deuxièmement, à même pH, les cinétiques d’hydrolyse étaient similaires entre ces deux concentrés et ainsi, les temps de coagulation dépendaient du degré d’hydrolyse au point de coagulation. Finalement, la troisième étude réalisée a permis de déterminer la contribution du lactose et des minéraux aux propriétés fromagères des concentrés RO et d’évaluer l’impact d’une modification des équilibres salins (déminéralisation de la micelle de caséines) des concentrés sur leurs propriétés fromagères. Les teneurs importantes en lactose et en minéraux ont été, conjointement, responsables des principales différences observées au niveau des propriétés de coagulation par la présure entre un concentré RO et UF. En revanche, seul le lactose était à l’origine de l’augmentation des rendements fromagers observée avec l’utilisation de concentrés RO. La déminéralisation de la micelle de caséine, via ajout de NaCl, a un impact négatif sur les propriétés fromagères des concentrés avec une perte de matière grasse marquée et une baisse des rendements fromagers, et n’est donc pas un moyen intéressant pour améliorer les propriétés fromagères des concentrés. Ce projet a permis d’apporter de nouvelles connaissances sur les concentrés laitiers produits par osmose inverse, et dans une moindre mesure par nanofiltration, et de mettre en évidence l’impact de ces procédés de concentration sur les propriétés fromagères des concentrés. La meilleure compréhension de ces systèmes laitiers et des facteurs affectant leurs caractéristiques permet de fournir des pistes à envisager pour optimiser leur utilisation en fromagerie. / The use of pressure-driven membrane processes is a common practice in the dairy industry, and ultrafiltration (UF) is widely used for the concentration of cheesemilk. Depending on how the UF concentrate is used, several advantages have been claimed, such as yield and productivity gains. Other membrane processes, such as reverse osmosis (RO) and nanofiltration (NF), are currently used for the management of effluents in the dairy industry and could be promising for cheesemilk concentration. Indeed, they are expected to lead to higher yield gains than UF concentrates, due to the concentration of all milk compounds and the retention of some of them in the cheese. In addition, the permeates generated contain essentially water and can be reused within the plant. However, only little information can be found about these types of milk concentrates and more knowledge is needed to consider their use for cheesemaking. The purpose of this project was therefore to characterize the milk concentrates from reverse osmosis and nanofiltration and to study their cheesemaking properties. A first study highlighted the impact of the milk concentration process on the physicochemical properties of the concentrates. It has been shown that the equilibria between the soluble and colloidal phases were not significantly affected by the concentration of milk, using UF, NF or RO. The latter two processes, on the other hand, have led to a decrease in pH and an increase in ionic strength and viscosity of the concentrates. At constant pH and similar protein content, rennet coagulation properties were affected by the type of concentrates used and, overall the UF concentrate had better coagulation properties than NF or RO concentrates. These differences were attributed to their high ionic strength and/or high viscosity. This first part, therefore, allowed us to have an overview of the impact of the concentration process on the concentrates characteristics and to highlight the differences in properties between various types of milk concentrates. A second study investigated the impact of the type of concentrate and pH adjustment on the rennet coagulation properties. The results obtained in the first part of the project showed the differences in coagulation times of UF and RO concentrates. To understand which parameter was responsible for those differences, the kinetics of κ- casein hydrolysis by rennet were studied. Two major results were highlighted. First, small pH variations allowed to obtain similar rennet coagulation kinetics between RO and UF concentrates, despite the significant differences in composition. Secondly, at the same pH, the hydrolysis kinetics were similar between these two concentrates and the differences in coagulation time were due to variation in the degree of hydrolysis at the coagulation point. Finally, the third study carried out highlighted the contribution of the high lactose and salts contents on the impaired cheesemaking properties of RO concentrates. Furthermore, the impact of a change in salt equilibrium (reduced micellar salt content) on the cheesemaking properties of milk concentrates was also studied. The high contents of lactose and salts were both responsible for the impaired rennet gelation properties of RO concentrates. However, the high lactose content alone was accountable for the increased cheese yields with the use of RO concentrates. Reducing the mineral charge of the micelles, via addition of NaCl, had a negative impact on the cheesemaking properties of concentrates with marked fat losses and decreased cheese yields. This approach is then not suitable to improve the cheesemaking properties of milk concentrates. This project provided new knowledge on milk concentrates produced by reverse osmosis, and to a lesser extent by nanofiltration, as well as on the impact of these concentration processes on the cheesemaking properties of the concentrates. The better understanding of these concentrates is necessary to optimize their use in cheesemaking.