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Several attempts have been made to combine the unique characteristics of graphene oxide (GO) and commercial polymers for successfully designing and fabricating next-generation membranes in filtration and separation technologies. The first part of the work develops a high flux polyethersulfone ultrafiltration membranes, by embedding GO sheets, starting from the polymer/GO solutions in ionic liquid and N, N dimethylformamide as co-solvents and promoting the pore formation via non-solvent induced phase separation. In the second part of the work, a protic ionic liquid was introduced as a solvent to disperse GO sheets and fabricate GO liquid crystal membranes for nanofiltration. The third part addresses the stability enhancement. GO membranes frequently disintegrate in aqueous environments due to swelling. Ethylenediamine was then used as a crosslinker, and the membranes were tested for organic solvent nanofiltration. Additionally, overcoming the permeation-rejection trade-off is challenging. Hence, the fourth work involved the intercalation of silica nanoparticles to form dual-sized nanochannels. In the final work, GO membranes were fabricated on the surface of hollow fibers to overcome scalability issues, by using a feasible spray coating method for efficient nanofiltration. Hollow fibers were crosslinked with hexamethylene diamine and GO was spray-coated on the crosslinked polymeric fibers for organic solvent nanofiltration. Overall, this study demonstrates the potential of GO in developing high-performance membranes for liquid separations relevant for industrial applications, such as wastewater treatment, food, chemical, petrochemical, and pharmaceutical processing.

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.

Throughout the United States, there are a large number of groundwater systems contaminated by chlorinated organic compounds. Of these compounds, carbon tetrachloride (CT) is one of the most frequently encountered due to its past, widespread industrial use. In anaerobic groundwater environments, CT has been shown to be susceptible to degradation by both biotic and abiotic processes. One abiotic process that has been researched extensively is the reduction of CT by iron metal and associated iron oxides and hydroxides. Magnetite, an iron oxide, is a ubiquitous component of many subsurface environments and has been investigated as a potential groundwater remediation technology. One beneficial characteristic of magnetite is the capability to be synthetically produced in various sizes and shapes - including particles within the nanoscale range. Nanoscale particles have been shown to be more reactive towards contaminants than larger sized particles due to their large surface areas and high surface reactivity. This project was designed to characterize the behavior of synthetic magnetite in the presence of carbon tetrachloride under anaerobic conditions. / Master of Science

Problemas ambientais causados pelo uso excessivo de energia proveniente do petróleo estão fazendo com que os países busquem a diversificação da matriz energética. Dentro deste contexto, é que a produção de biodiesel, a partir de óleos vegetais, vem se destacando no cenário energético. A extração da matéria-prima usada na produção desses biocombustível é uma fase de extrema importância, por isso, faz-se necessário determinar qual a melhor forma de sua realização, caracterizando os principais fatores químicos e físicos que interferem nesse processo. Visando otimizar o processo de extração do óleo do caroço do pequi, este trabalho baseou-se na realização de experimentos que buscaram identificar o teor aproximado de óleo no caroço do pequi e ainda qual o melhor solvente orgânico, entre hexano, etanol e a mistura desses solventes, para a extração do óleo do caroço do pequi para a produção de biodiesel. A partir dos dados obtidos nos ensaios realizados neste trabalho, pode ser observado que o putâmem do pequi apresenta um teor elevado de óleo, em méidia de 31%, quantidade superior a encontrada no grão da soja, que hoje é a matéria – prima base para a produção de biodiesel. Observou-se ainda que a misturas dos dois solventes orgânicos (hexano + etanol) na razão de 1:1 mostrou-se mais eficiente no processo extraíndo aproximadamente 34% do óleo presente no caroço do pequi. / The environmental problems caused by the excessive use of energy from petroleum are causing countries seek to diversify sources of energy. Within this context, is that the production of biodiesel from vegetable oils, has been increasing in energy scenario. The extraction of the raw material used in producing these biofuels is an extremely important step, so it is necessary to determine the best form of his achievement, featuring the main chemical and physical factors that affect this process. In order to optimize the extraction process of oil pits pequi, this work was based on the realization of experiments that attempted to identify the approximate oil content in the pits pequi and yet which is the best organic solvent, hexane between ethanol and the mixture of these solvents for oil extraction from the seed pequi for biodiesel production. Starting from the data obtained in the tests performed in this study, it can be observed that the pits pequi has a high content of oil, around 31%, much higher than found in soy beans, which today is raw - material basis for biodiesel production. It was also observed that mixtures of two organic solvents (hexane + ethanol) at a ratio of 1:1 was more efficient in the process of Extracting approximately 34% of the oil present in the pits pequi.

The further usage of vegetable and plant waste from juice pressing industry as textile dyes is presented in this thesis. The thesis is focused on β-carotene (C40H56) dyestuff extracted from orange peel and carrot residue. The three organic solvents; ethyl acetate, petroleum ether and hexane/acetone (1:1 v/v) were used for the extraction. The analysis of the extract was done by RP-HPLC with a C18 column. The yield and the purity of the extracted β-carotene were determined. The highest yield was achieved with petroleum ether whereas the other two solvents were nearly as good. The highest and purest amount on β-carotene was found in the extracts of carrots. The dyeing process was continued with β-carotene dyestuff of orange peel and carrot residue extracted from 27 g of residue on 0,8 g cotton in the dyeing ratio 1:50. Unmordant and post mordanted bleached and mercerized cotton fabric was dyed. 10% alum of the weight fraction of cotton was used as mordant. Colour measurements (K/S, C*, L*, a*, b*, h and ΔE) and fastness properties as light- (ISO-Norm B02) and wash fastness (ISO 105 – C) were tested. Fair light fastness grades were achieved by β-carotene dyestuff of orange peel residue dyed on cotton fabric. Poorer were the grades for β-carotene dyestuff of carrot residue for both unmordanted and mordanted samples. The wash fastness couldn’t achieve reasonable results neither for β-carotene dyestuff from carrots nor orange peel residue, dyed on cotton fabric. / Program: Master programme in Textile Engineering

The aim of the dissertation to study small organic solute rejection in organic solvent nanofiltration using cheminformatics and machine learning. Chemically diverse datasets were curated using a novel medium high-throughput methodology and literature data extraction. These datasets contained thousands of datapoints of small organic solute rejections and process parameters. Different chemical fingerprinting has been used for feature generation, such as molecular descriptors, Morgan fingerprints, and latent-vector representation. These features were used to train different machine learning models, such as graph neural networks, partial least squares regression, and boosting tree algorithms. The obtained models were used to predict small organic solute rejection for nanofiltration related applications. Correlation between rejection and the molecular descriptors have been studied to deepen the understanding of transport and rejection through polymeric membranes. Explainable artificial intelligence concept was used to study the effect of solute, solvent and membrane structure on solute rejection. The conclusion of the dissertation highlights the importance of the chemical structure effect in nanofiltration and provides a future perspective on data-driven approached for nanofiltration and organic solvent nanofiltration.

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In order to meet the energy needs of a growing world in a sustainable manner, new high efficiency, carbon-neutral fuels and chemical feedstocks are required. An emerging approach that shows promise for high efficiency production of renewable fuels and chemicals is the use of purified enzymes combined in one pot to catalyze complex conversions: synthetic pathway biotransformations (SyPaB). An exemplary technology in this burgeoning field is the production of hydrogen from biomass sugars. Lignocellulosic biomass, which includes agricultural residues, energy crops, and industrial waste streams, is an ideal substrate for SyPaB conversion, as it is abundant and cheap, second only to untaxed coal on a $/energy content basis. But the structure of biomass is highly recalcitrant, making high-yield biological conversion difficult to achieve. In order to increase susceptibility to enzymatic digestion, thermochemical pretreatments are applied, with the goals of removing of lignin, the simplest example being soaking in aqueous ammonia (SAA); hemicellulose removal, most often using dilute acid (DA); and increasing cellulose accessibility by cellulose solvent-based pretreatments, such as cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF). In a comparison of the lignin removal (SAA) and accessibility increase (COSLIF) approaches, we found that certain levels of lignin removal (~15%) were important, but further lignin removal was less effective at achieving digestibility gains than increasing cellulose accessibility. Pretreated biomass forms an excellent substrate for SyPaB hydrogen generation, due to low cost and high sugar content. Following experiments demonstrating the high yield conversion of sucrose to hydrogen (97%) and SyPaB generation of hydrogen at a rate commensurate with the best biological rates achieved, 157 mmol/L/h. SyPaB was combined with enzymatic hydrolysis to enable the direct conversion of cellulosic biomass, including untreated, DA, and COSLIF corn stover. In addition, an updated kinetic model of the system was used to rationally increase the maximum hydrogen production rate by 70% while minimizing total enzyme loading and without increasing substrate concentration. Together, these results demonstrate the high level of engineering control in cell-free systems, which can enable conversion of a variety of substrates to hydrogen at the highest possible yield and rates as high as any biohydrogen production method. / Ph. D.