Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / The development of products with antimicrobial, inhibitory or even lethal action has attracted considerable attention in widely different research and applications fields. The present work studies the obtaining of an antimicrobial material derived from activated carbon submitted to adsorption in a medium with silver ions. It s divided into five chapters, dealing respectively of: introduction (subject s delimitation; research objectives; study s structure); literature review (antimicrobial materials, metal ions, activated carbon impregnated with silver (ACIS); ACIS s details of obtaining and applications); materials and methods (type of research, experiments, characterization tests); results and discussions and conclusions. To characterize the material obtained, in addition to the surface area analysis, inhibitory and bactericidal effects of the samples were evaluated by microbiological testing with different bacteria. About the experimental methodology, it was tested the effects of the silver ions impregnated on coal in cultures of bacteria Escherichia coli and Staphylococcus aureus from different strains. These effects were evaluated by minimum inhibitory concentration and minimum bactericidal concentration tests. The results for the material obtained confirmed the action of silver as an important antibacterial agent. / O desenvolvimento de produtos com ação antimicrobiana, inibitória ou mesmo letal, tem atraído considerável atenção nos mais distintos campos de pesquisa e aplicações. O objetivo deste estudo foi obter um material antimicrobiano a partir de carvão ativado submetido à adsorção em um meio com íons de prata. O trabalho está dividido em cinco capítulos, tratando respectivamente de: introdução (delimitação do tema; objetivos da pesquisa; estrutura do estudo); fundamentação teórica (materiais antimicrobianos; íons metálicos; carvão ativado impregnado com prata (CAIP); detalhes de obtenção e aplicações do CAIP); materiais e métodos (tipo de pesquisa; experimentos; testes de caracterização); resultados e discussões e considerações finais da autora. Para a caracterização do material obtido, além de análise de área superficial, avaliaram-se os efeitos inibitório e bactericida das amostras através de testes microbiológicos com diferentes bactérias. Quanto à metodologia experimental aplicada, foram testados os efeitos da presença de íons de prata no carvão em culturas de bactérias Escherichia coli e Staphylococcus aureus de diferentes cepas. Tais efeitos foram avaliados através de testes de concentração mínima inibitória e concentração mínima bactericida. Os resultados referentes ao material obtido confirmaram a ação da prata como um importante agente antibacteriano.

The increased demand of fossil fuel along with the depletion of economical crude oil resources, environmental challenges such as the accumulation of CO2 and other greenhouse gases in the atmosphere and the reduction of the dependence on imported oil are some of the motivations for the huge interest in biofuels. Biobutanol produced from ABE fermentation has been considered to be a good partial replacement for fossil fuels. However, challenges such as the need for inexpensive feed-stocks, improved fermentation performance to achieve higher final butanol concentration and higher yield, an efficient method for solvent recovery, and water recycle are the main obstacles to make the production of this alcohol economically viable. Pervaporation, a membrane-based process, is considered to be an attractive separation method to remove butanol from ABE fermentation broth. Among the membranes used for butanol separation, PDMS membranes showed reasonable performance such as good permeability, and appropriate selectivity for butanol separation by pervaporation. However, PDMS membranes need to be improved in terms of performance to be applicable in large scale butanol production plants. In this study, activated carbon nanoparticles have been embedded into the matrix of the PDMS membrane to improve its separation performance and, in particular, the permeation flux and butanol selectivity. Result showed that the presence of nanoparticles improves the PDMS membrane performance up to a certain particle loading. Moreover, it was shown that the operating conditions have a major impact on the pervaporation membrane separation process. The best membrane for pervaporation separation of butanol from binary aqueous solutions was obtained for a 6 wt% particle concentration where the total permeation flux and butanol selectivity increased by 42.6% and 51.9%, respectively, compared to neat PDMS membranes. Moreover, the best performance for the separation of butanol from ABE model solutions was achieved for an 8 wt% nanoparticle loading. Both the selectivity for butanol and the total permeation flux more than doubled in comparison to neat PDMS membranes prepared in this study. Moreover, in order to compare the PDMS/AC mixed matrix membrane performance for pervaporation separation of butanol from binary and ABE model solutions with PDMS membranes available on the market, experiments were also performed with a commercial PDMS membrane. Result of butanol separation from ABE model solutions showed that mixed matrix membranes with 8 wt% nanoparticles loading had a higher permeation flux than that of the commercial membranes. It was clearly shown that the presence of activated carbon nanoparticles in the matrix of the PDMS would be beneficial for the pervaporation separation of butanol from ABE fermentation broths. To better comprehend how the presence of activated carbon nanoparticles in the polymeric membranes enhance the performance of the membranes, a series of numerical simulations were performed. A finite difference model was developed to simulate the mass transfer of permeating components through mixed matrix membranes by pervaporation for a wide range of relative permeability, nanoparticle loading, particle shape, particle size and different filler adsorption isotherms. Finally, an investigation has been performed to optimize the butanol pervaporation separation process from ABE fermentation broth at an industrial scale.

Os desreguladores endócrinos, como o bisfenol A (BPA), são compostos encontrados na água em concentrações da ordem de μg.L-1 ou ng.L-1, sendo por isso também denominados micropoluentes. Sua presença, mesmo em baixas concentrações, pode causar prejuízos aos organismos expostos. Neste contexto, o objetivo do presente trabalho foi avaliar a remoção de BPA por membranas de ultrafiltração (UF) e osmose inversa (OI) e por carvão ativado granular (CAG). Essas técnicas têm a vantagem de não gerar subprodutos que também podem ser tóxicos. Nos estudos foram realizados experimentos para remoção do BPA através de membrana PL-1 (celulose regenerada de 1 kDa), Sy-10 (polietersulfona de 10 kDa) e membrana de OI (poliamida) reutilizada, com concentração inicial de 500 μg.L-1 de BPA. Para a membrana Sy-10, foram testados os pHs 7 e 10. Os ensaios de adsorção foram realizados com CAG (1-2mm) em frascos contendo 100 mL da solução de BPA, com 0,5 g de CAG para cada frasco. As variáveis testadas foram pH, tempo de contato e concentração inicial na ordem de mg.L-1. Adicionalmente, foi testada a concentração inicial de 500 μg.L-1 de BPA em experimento de adsorção. Os resultados obtidos mostraram que a capacidade da membrana Sy-10 para remoção de BPA foi superior, chegando a cerca de 90% de remoção, em contraposição aos 20% encontrados para PL-1. A membrana de OI apresentou remoções de cerca de 95%. A influência do pH (7 e 10) na remoção do BPA para a membrana Sy-10 não mostrou-se significativa. Nos ensaios de adsorção, analisando diferentes valores de pH, obteve-se eficiência de 93% para pH 7. Ensaios de variação do tempo de contato com CAG mostraram que o equilíbrio é atingido nos primeiros 10 minutos para a maior concentração e em 40 minutos para a menor concentração testada, de 500 μg.L-1. O estudo do efeito da concentração inicial de BPA na adsorção mostrou que a remoção aumenta com o aumento da concentração inicial do poluente. Conclui-se que tanto a adsorção em CAG quanto membranas são boas alternativas para a remoção de BPA de soluções aquosas. As duas técnicas poderiam ser usadas conjuntamente, sendo que o concentrado do processo com membranas poderia ser submetido à adsorção por CAG. / Endocrine disrupting chemicals, such as bisphenol A (BPA) compounds, are found in water at concentrations of the order of μg.L-1 or ng.L-1 is therefore also known micropollutants. His presence, even at low concentrations, can cause damage to exposed organisms. In this context, the aim of this study was to evaluate the removal of BPA by ultrafiltration (UF) and reverse osmosis (RO) membranes and granular activated carbon (GAC). These techniques have the advantage of not generating by-products can also be toxic. In the studies were performed experiments to remove the BPA by PL-1 (1 kDa regenerated cellulose), Sy-10 (10 kDa polyethersulfone) and RO (polyamide) reused membranes, with initial concentration of 500 μg.L-1 of BPA. For Sy-10 membrane pHs 7 and 10 were tested. The adsorption experiments were carried out with GAC (1-2mm) in flasks containing 100 mL of the BPA solution and 0.5 g of GAC to each vial. The variables tested were pH, contact time and initial concentration on the order of mg.L-1. Additionally, we tested the initial concentration of 500 μg.L-1 of BPA in adsorption experiment. Results showed that the capacity of Sy-10 membrane to remove BPA was higher, reaching approximately 90% removal, as opposed to the 20% found to PL-1. The RO membrane showed removal of about 95%. The influence of pH (7 and 10 ) in the removal of BPA onto the membrane Sy - 10 was not significant. In adsorption tests, analyzing different pH values was obtained efficiency from 93% to pH 7. Testing time variation of contact GAC showed that equilibrium is reached in the first 10 minutes to the largest concentration and 40 minutes to the lowest concentration tested, 500 μg.L-1. The study of the effect of the initial concentration of BPA in the adsorption showed that removal increases with increase in the initial concentration of the pollutant. It was concluded that both the GAC adsorption as membranes are good alternatives for the removal of the BPA aqueous solutions. The two techniques could be used together, with the concentrate from the membrane process could be subjected to adsorption GAC.

Orientador: Antonio Carlos Luz Lisboa / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-27T17:27:40Z (GMT). No. of bitstreams: 1 Rombaldo_CarlaFabianaScatolim_D.pdf: 2818147 bytes, checksum: eb790e05e31dc621e11ca7ea1a4eb2d7 (MD5) Previous issue date: 2015 / Resumo: As fibras obtidas diretamente de fonte animal, mineral e vegetal são definidas como fibras naturais, sendo as mais comuns: a lã, o linho, o rami, o sisal, a juta, entre outras. Essas fibras têm uma importância social muito forte em países tropicais, especialmente na geração de empregos na zona rural e em áreas economicamente deprimidas. As fibras naturais, em sua maioria, são leves, resistentes, não abrasivas, renováveis, biodegradáveis e recicláveis, características que permitem competir com outros materiais artificiais que tenham problemas de disponibilidade ou ambientais. Além dos compósitos desenvolvidos com fibras naturais, existem ainda os carvões ativados que se destacam como um material com elevada porosidade e alta capacidade de adsorção, tanto em fase liquida quanto em fase gasosa. Visando o aproveitamento de recursos naturais disponíveis no território nacional e buscando alternativas que sejam economicamente viáveis para a produção de carvão ativado (CA), o presente trabalho teve como objetivo geral utilizar as fibras de juta e as fibras de sisal como matérias-primas para a produção de CA. Os CAs produzidos foram testados para a remoção de benzeno em solução aquosa. A produção do CA foi baseada na carbonização e na ativação física com CO2 e vapor d¿água. Para avaliar a evolução da estrutura porosa dos CAs obtidos foi utilizada a técnica de adsorção de N2 a 77K. Os resultados indicaram a possibilidade de produzir um material poroso com uma combinação de estrutura micro e mesoporosa, dependendo dos parâmetros utilizados nos processos de carbonização e ativação. Foram realizados alguns ensaios de adsorção das frações solúveis da gasolina em água, tanto com os CAs provenientes das fibras naturais, juta e sisal, como em CAs comerciais. Foi possível observar que o CA proveniente da fibra de juta se mostrou tão eficiente quanto o CA comercial. / Abstract: The fiber obtained directly from animal, mineral and vegetable are defined as natural fibers, and the most common are: wool, linen, ramie, sisal, jute, and others; which have very strong social importance at tropical countries, especially for job creation in rural and economically poor areas. These fibers are lightweight material, resistant, non-abrasive, renewable, biodegradable and recyclable. Features that allow it compete with other artificial materials, which have availability or environmental problems. In addition to the natural fiber composites there are activated carbons which stand out as high porosity material with high adsorption capacity of liquid and gas phases. Aiming at the use of natural resources available in the country and seeking for alternatives that are economically viable for activated carbon production, this study has investigated the possibility of using jute fiber and sisal fiber as precursors for the production of activated carbon (AC). The produced AC were characterized and tested for benzene adsorption in aqueous solution. The AC production of was based on the carbonization and physical activation with CO2 and steam. To evaluate the porous structure of the produced activated carbon N2 adsorption at 77K was used. The adsorption results indicated the possibility of producing a porous material having a combination of micro and mesoporous structure, depending on the parameters used in the carbonization and activation processes. The water-soluble gasoline fraction adsorption experiments using natural fibers and commercial AC showed that both are equally efficient / Doutorado / Engenharia de Processos / Doutora em Engenharia Quimica

O processo de adsorção vem sendo utilizado como uma técnica eficaz para a remoção de íons metálicos em efluentes. Neste trabalho são apresentados os estudos para avaliar da capacidade de adsorção de cobalto em caulinita, um adsorvente de baixo custo, visando à remoção deste íon de soluções aquosas. Foi analisada a área superficial específica (S) em 25 amostras de materiais preparadas de diferentes modos: caulinita, bentonita e carvão ativado e, misturas de caulinita-bentonita e caulinita-carvão ativado. Estas misturas foram preparadas pela adição de 10, 20, 30, 40 e 50% de carvão ativado ou bentonita à caulinita. As amostras de caulinita-carvão ativado e caulinita in natura foram calcinadas a 600 e 1000 °C por 4 horas. Foi escolhida para os testes de adsorção a mistura de caulinita com 10% de carvão ativado por apresentar a melhor relação custo benefício em relação à S. Os parâmetros de adsorção investigados nesta mistura foram: tempo de contato, pH, concentração inicial de soluto, competição iônica e força iônica. Verificou-se que o tempo de contato e o pH otimizados para o propósito do trabalho foram 30 min e pH 6. Nestas condições a eficiência de remoção do íon cobalto da solução foi superior a 80%. Verificou-se que a presença de íons Cr e Zn, bem como o aumento da força iônica diminuem a capacidade de adsorção do Co na mistura adsorvente. As isotermas de Langmuir e Freundlich apresentaram R2 iguais a 0,906 e 0,597, respectivamente. Os parâmetros determinados nestas isotermas indicaram um processo espontâneo, ou seja, energeticamente favorável, para a adsorção do Co nas condições e que foram realizadas este trabalho. / The adsorption process has been used as an efficient technique for the removal of metallic ions in industrial effluent. In this work, it is presented the studies to evaluate the adsorption capacity of cobalt in kaolinite, a low cost adsorbent, aiming at the removal of this ion from aqueous solutions. The specific surface area (S) was analyzed in 25 samples prepared in different ways: kaolinite, bentonite and activated carbon and, mixtures of kaolinite-bentonite and kaolinite-activated carbon. These mixtures were prepared by adding to kaolinite 10, 20, 30, 40 or 50% of activated charcoal or bentonite. Samples of kaolinite-activated charcoal mixture and raw kaolinite were also calcined at 600 and 1000 °C for 4 hours. The adsorption parameters investigated for these adsorbents were: contact time, pH, solute initial concentration, ionic competition and ionic strength. It was found that the optimized contact time and pH, for the purpose of this work, were 30 min and pH 6. Under these conditions the cobalt ion removal efficiency was greater than 80%. It was verified that the presence of Cr and Zn ions, as well as the increase in ionic strength caused a decrease in the adsorption capacity of Co in the adsorbent mixture. The Langmuir and Freundlich isotherms presented R2 equal to 0.906 and 0.597, respectively. The parameters determined by these isotherms indicated a spontaneous process, i.e., energetically favorable, for the adsorption of Co under the conditions that this work was carried out.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Macadamia activated carbon (MAC) was impregnated with different concentrations of nitric acid and heated under reflux to improve the structural characteristics of the adsorbent for both considerable reduction and enhanced removal of Cr(VI). The chemical oxidation of ACs increased the surface oxygenated functional groups. Adsorption of Cr(VI) was carried out by varying parameters such as contact time, pH, concentration, and adsorbent dosage. The optimum operating conditions for the adsorption of Cr(VI) were pH 1, contact time 240 min, adsorbent dosage 10.67 g/L and Cr(VI) concentration 100 mg/L. The results showed that the Macadamia–based AC could be used efficiently for the treatment of chromium-containing solutions as a low-cost alternative compared to commercial AC and other adsorbent reported. The results showed that treated MAC performed better than untreated MAC, signifying the effect of secondary treatment on the enhanced removal of pollutants. Comparable to the application of ACs is the development of imprinting technologies for selective metal ion remediation in environmental samples. The combination of ion imprinting effects and functionalized carbon adsorbents produce materials which effectively remove and selectively recognize the target analyte. Macadamia activated carbon (MAC) was chemically pre-treated with nitric acid to generate carboxyl groups on the surface. The carboxylated MAC was then reacted with triethylenetetramine, N,N’-diisopropylcarbodiimide and CrCl3.6H2O to produce MACN20-imprinted sorbents (MACN20-IIP). MACN20-non imprinted (MACN20-NIP) counterparts were prepared, but Cr3+ was excluded in the synthesis. Alteration of surface structural characteristics and characterization of prepared adsorbents as confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, Brunauer–Emmett–Teller and scanning electron microscopy. MACN20-IIP and MACN20-NIP adsorbents were evaluated for their Cr3+ uptake from aqueous solution in batch format. Maximum conditions were achieved at pH 5, 50 mg/L Cr(III) initial concentration and 33.33 g/L of adsorbent dosage. Presence of co-ions slightly diminished the removal of Cr(III) by MAC-IIP adsorbents. Application of the MACN20-IIP and MACN20-NIP on spiked acid mine drainage artificial sample led to collapse in the removal efficiency of MACN20-NIP while MACN20-IIP still showed good removal efficiencies. These results demonstrated that surface imprinting led to better adsorption rates and capacity. The data was better described by the Freundlich multilayer adsorption and pseudo-second order kinetic rate model. The combination of both the carbon sorbent and the surface-mediated IIPs effectively improved total chromium remediation in aqueous systems.

This work deals with bio gas cleaning by a PSA method and modernizing of a laboratory unit. Raw bio gas contains many unwanted elements like carbon dioxide mostly which lowers its energy potential then. To extend the possibilities of usage of bio gas it is necessary to remove such elements. One of the well-known method for eliminating CO2 out of the bio gas is the method called Pressure Swing Adsorption (PSA). This work describes PSA method and compares it with other methods for cleaning the bio gas. In the following part of my work I am introducing the original laboratory PSA unit which is placed in the laboratory of UPI institution for research purposes. The modernization of the method was made by changing the manual valves for electromagnetic ones and there was also designed a new control system unit for two control modes. For manual and for automatic. The essential function is based on remote controlling the valves either by switches or by a program. The electric control panel was created for such required modes. The automated process was controlled by Arduino programming platform which was integrated into the panel. In the case of the next measurement and reading there was created a detailed description for user on how to operate the control panel and also the comments for control program of automatization.

This diploma thesis deals with the effectiveness of selected adsorbents for the removal of micropollutants from drinking water. In the first part there are described individual types of micropollutants and their occurrence in water. Further, there are described pharmaceuticals and their consumption in the world. At the end of the first part, the possibilities of removing micropollutants in drinking water treatment are approached and two water treatment plants in the Czech Republic have been selected, which already use the technology of the removal of some micropollutants. In the practical part of this diploma thesis is performed an experiment of removal of Ibuprofen from model water by adsorption on selected materials, which are Filtrasorb F100, Bayoxide E33 and GEH.

The subject of the thesis is the issue of pesticides in the environment and the possibility of their removal through activated carbon. The thesis is divided into two parts, the search part and the practical part. The research part is focused on description of activated carbon. It also deals with the distribution of pesticides and their degradation in the environment. In the practical part, a laboratory experiment was carried out to determine the effectiveness of removing pesticides and metabolites from the test water on two types of activated carbon.

This diploma thesis deals with sorption properties of biochar produced from wood biomass treated with concentrated hydrochloric acid and activated carbon with respect to the triazine pesticide propazine. Although pesticides are widely used in both agriculture and the private sector worldwide, they pose a significant risk to ecosystems and human health. Propazine belongs to the group of chlorinated triazine herbicides, which pose a risk mainly as endocrine disruptors. The sorption of organic pollutants using pyrogenic carbonaceous materials promises an efficient and economically affordable solution, which has recently received increasing attention from the scientific community. In this work, we used isotherms to describe the equilibria of propazine sorption to given sorbents during vial experiments. Analysis of the propazine content in the model water solutions after reaching equilibrium was performed using high-performance liquid chromatography with mass detection.