Biofuel is a renewable and sustainable energy source with near-neutral carbon footprint. Algae are an ideal feedstock for biofuel production because they reproduce quickly and have high oil. Algae can be cultivated in non-arable land, and would not impact the food supply. Unfortunately, processing algae into biofuel is more expensive than land crops due to the large volumes of dilute algal suspension that must be harvested and concentrated. In order to improve algae-based biofuel economics, resins were developed that reduce costs associated with water pumping and transport. Hydrophobic resins were developed for binding oil out of an algal suspension so that the residual biomass could be recovered without solvent contamination. Binding behavior displayed lipid species specificity, and binding capacity was improved by ethanol treatment of the biomass. Algae was harvested by binding to anion exchange resin and directly converted into biodiesel. One-step, room temperature in situ transesterification of algae yielded nearly as much biodiesel as two-step, heated transesterification of dried biomass. Elution with transesterification reagent also regenerated the resin for subsequent algal binding. Functionalized resins were developed with high algal binding capacity at neutral pH. Binding was easily reversed, as treatment with buffer with pH higher than pKa of the resin functional group removed the algae and regenerated the resin for subsequent use. The resin bound 10% of its weight in algae and released it as a 100-fold concentrated suspension. The polymers developed can be scaled up for commercial processes and reduce algal harvesting and concentration costs. / text

This study focuses on the development of novel two-stage esterification-transesterification synthesis of biodiesel from used cooking oil (UCO) using novel heterogeneous catalysts. The esterification of the UCO was investigated using three types of ion exchange resins catalysts including Purolite D5081, Purolite D5082 and Amberlyst 15. Of all the catalysts investigated, Purolite D5081 resin showed the best catalytic performance and was selected for further optimisation studies. From the optimisation study, it was found that the external and internal mass transfer resistance has negligible effect on the esterification reaction. At the optimum reaction conditions, Purolite D5081 achieved 92% conversion of FFA. During reusability study, the conversion of FFA dropped by 10% after each cycle and it was found that progressive pore blockage and sulphur leaching were dominant factors that decreased the catalytic performance of the Purolite D5081 catalyst. A kinetic modelling for FFA esterification was carried out using Purolite D5081 as a catalyst. Three types of kinetic models were investigated i.e. pseudo homogeneous (PH), Eley-Rideal (ER) and Langmuir-Hinshelwood-Hougen-Watson (LHHW). Experimental data obtained from the batch kinetic studies was successfully represented by the PH model and a good agreement between experimental and calculated values was obtained. The activation energy for esterification and hydrolysis reaction was found to be 53 and 107 kJ/moL. The transesterification of pre-treated cooking oil (P-UCO) was investigated using various types of heterogeneous catalysts including Purolite CT-122, Purolite CT-169, Purolite CT-175, Purolite CT-275, Purolite D5081, Diaion PA306s and Cs-supported heteropolyacids catalysts. Of all the catalysts investigated, Diaion PA306s catalyst showed the highest conversion of triglycerides and was selected for further optimisation studies. At the optimum reaction conditions, Diaion PA306s achieved ca. 75% of triglycerides conversion. During the reusability study, Diaion PA306s catalyst gave a similar conversion of triglycerides after being reused once. Therefore, it was concluded that the resin can be used several times without losing catalytic activity. Several purification methods have been investigated and dry washing method was chosen as the best alternative for biodiesel purification.

Não há dúvidas que a exitosa exploração do Cerrado só foi possível graças às pesquisas que desenvolveram tecnologias de correção e adubação específicas para esse ambiente. Apesar de estar consolidado como um dos principais ambientes de produção agropecuária do mundo, as pesquisas devem avançar contribuindo, cada vez mais, com aumento na eficiência do uso do fósforo (P), por ser o elemento mais limitante para produção agrícola nesse ambiente. Devido às características dos solos dessa região, parte do P aplicado é retido pelo solo em formas que as plantas não conseguem absorver, resultando na acumulação de quantidades significativas do nutriente no solo. Apesar de não ser um assunto relativamente novo e do grande número de trabalhos, o tema avaliação da disponibilidade de fósforo do solo ainda provoca dúvidas. Além dos estudos em que é avaliada a eficiência de diversos extratores como Mehlich-1 e resina de troca aniônica, outras técnicas passaram a ser utilizadas para esse fim. Estudos objetivando avaliar a distribuição (dinâmica) do fósforo nas diferentes frações do solo e as mudanças nessa distribuição em função do manejo aplicado aos cultivos e, também, do tempo de cultivo, têm sido conduzidos com crescente intensidade. Estudos também têm sido conduzidos buscando identificar as formas de acumulação de P no solo. Para isso, modernas técnicas espectroscópicas, como por exemplo, a espectroscopia baseada em luz synchrotron, têm sido utilizadas como uma poderosa ferramenta, auxiliando na identificação dos compostos presentes no solo. Face ao exposto, objetivou-se avaliar as alterações no fósforo disponível e nas frações e formas de fósforo em solo de Cerrado submetido ao manejo em semeadura direta com diferentes tempos de cultivo. Foram coletadas amostras compostas em quatro áreas que se encontravam no momento da coleta com 5, 8, 12 e 18 anos de cultivo desde a abertura das áreas, e também numa área sob vegetação nativa. O fósforo disponível foi extraído por Mehlich-1 e resina de troca aniônica. As amostras foram submetidas ao fracionamento químico de fósforo e espectroscopia de alta resolução da borda de absorção (XANES - X-ray absorption near edge structure). Observou-se que, de maneira geral, os teores de fósforo no solo foram sempre mais altos nas áreas cultivadas, principalmente na camada superficial, em comparação aos da área com vegetação nativa, o que reflete o impacto das adubações fosfatadas. A aplicação superficial do fertilizante fosfatado gerou nítidos gradientes de P no perfil do solo, principalmente para as frações lábeis e moderadamente lábeis, sendo essas frações as que sofreram maior influência do fertilizante quando comparadas às frações de menor disponibilidade. Considerando-se os mesmos extratores, os teores das frações orgânicas foram maiores em comparação às correspondentes frações inorgânicas. As formas de fósforo nos solos estudados foram predominantemente associadas ao alumínio e ao ferro, com destaque para o nutriente associado ao alumínio, sendo que, com o ferro, a associação ocorreu predominantemente por meio de fenômenos de adsorção em detrimento de fenômenos de precipitação. / There is no doubt that the successful exploitation of the Cerrado was only possible due to the research that developed specific correction and fertilization technologies to this particular environment. Due to the characteristics of soils in the region, part of applied phosphorus (P) is retained by the soil in plant unavailable forms, resulting in accumulation of significant amounts of nutrient in the soil. Despite not being a relatively new issue and the large number of research performed on this topic, the assessment of the soil P availability still raise important questions. In addition to studies in which the efficiency of various extractants have been tested, such as Mehlich-1 and anion exchange resin, other techniques are being used for this purpose. Studies for evaluating the P distribution (dynamic) in different soil fractions and the changes in this fractions due to the management applied to crops and also the time of cultivation have been conducted with increasing intensity. Studies have also been carried out in order to identify the forms of P accumulation in soils. For this purpose, modern spectroscopic techniques such as spectroscopy based on synchrotron light source, have been used as a powerful tool, assisting in the identification of P compounds presents in the soil. The aims of this study were to evaluate the changes in available, fractions and forms of P in soils of Cerrado with different times under no-till cultivation system. Composite soil samples were collected in four areas under 5, 8, 12 and 18 years of no-till cultivation since the areas were opened, and also in a area under native vegetation. The soil in the area was classified as Typic Hapludox and the areas were cultivated alternating crops of soybeans, corn and cotton. Available P was extracted by Mehlich - 1 and anion exchange resin. The samples were subjected to Hedley´s chemical fractionation of P and X- ray absorption near edge structure (XANES). It was observed that, in general, the levels of P in the soil were always higher in cultivated areas, mainly in the topsoil, when compared to the area under native vegetation, which reflects the impact of phosphate fertilization. Surface application of phosphate fertilizer produced sharp gradients of P in the soil profile, especially for both labile and moderately labile fractions, and these fractions suffered the greatest influence of fertilizer compared to fractions of lower availability. Considering the same extractants, the organic P fractions contents were higher compared to the corresponding inorganic fractions. Forms of phosphorus in soils were predominantly associated with aluminum (Al) and iron (Fe), especially P associated with Al, and with Fe the association occurred predominantly through adsorption phenomenon rather than precipitation reactions.

Não há dúvidas que a exitosa exploração do Cerrado só foi possível graças às pesquisas que desenvolveram tecnologias de correção e adubação específicas para esse ambiente. Apesar de estar consolidado como um dos principais ambientes de produção agropecuária do mundo, as pesquisas devem avançar contribuindo, cada vez mais, com aumento na eficiência do uso do fósforo (P), por ser o elemento mais limitante para produção agrícola nesse ambiente. Devido às características dos solos dessa região, parte do P aplicado é retido pelo solo em formas que as plantas não conseguem absorver, resultando na acumulação de quantidades significativas do nutriente no solo. Apesar de não ser um assunto relativamente novo e do grande número de trabalhos, o tema avaliação da disponibilidade de fósforo do solo ainda provoca dúvidas. Além dos estudos em que é avaliada a eficiência de diversos extratores como Mehlich-1 e resina de troca aniônica, outras técnicas passaram a ser utilizadas para esse fim. Estudos objetivando avaliar a distribuição (dinâmica) do fósforo nas diferentes frações do solo e as mudanças nessa distribuição em função do manejo aplicado aos cultivos e, também, do tempo de cultivo, têm sido conduzidos com crescente intensidade. Estudos também têm sido conduzidos buscando identificar as formas de acumulação de P no solo. Para isso, modernas técnicas espectroscópicas, como por exemplo, a espectroscopia baseada em luz synchrotron, têm sido utilizadas como uma poderosa ferramenta, auxiliando na identificação dos compostos presentes no solo. Face ao exposto, objetivou-se avaliar as alterações no fósforo disponível e nas frações e formas de fósforo em solo de Cerrado submetido ao manejo em semeadura direta com diferentes tempos de cultivo. Foram coletadas amostras compostas em quatro áreas que se encontravam no momento da coleta com 5, 8, 12 e 18 anos de cultivo desde a abertura das áreas, e também numa área sob vegetação nativa. O fósforo disponível foi extraído por Mehlich-1 e resina de troca aniônica. As amostras foram submetidas ao fracionamento químico de fósforo e espectroscopia de alta resolução da borda de absorção (XANES - X-ray absorption near edge structure). Observou-se que, de maneira geral, os teores de fósforo no solo foram sempre mais altos nas áreas cultivadas, principalmente na camada superficial, em comparação aos da área com vegetação nativa, o que reflete o impacto das adubações fosfatadas. A aplicação superficial do fertilizante fosfatado gerou nítidos gradientes de P no perfil do solo, principalmente para as frações lábeis e moderadamente lábeis, sendo essas frações as que sofreram maior influência do fertilizante quando comparadas às frações de menor disponibilidade. Considerando-se os mesmos extratores, os teores das frações orgânicas foram maiores em comparação às correspondentes frações inorgânicas. As formas de fósforo nos solos estudados foram predominantemente associadas ao alumínio e ao ferro, com destaque para o nutriente associado ao alumínio, sendo que, com o ferro, a associação ocorreu predominantemente por meio de fenômenos de adsorção em detrimento de fenômenos de precipitação. / There is no doubt that the successful exploitation of the Cerrado was only possible due to the research that developed specific correction and fertilization technologies to this particular environment. Due to the characteristics of soils in the region, part of applied phosphorus (P) is retained by the soil in plant unavailable forms, resulting in accumulation of significant amounts of nutrient in the soil. Despite not being a relatively new issue and the large number of research performed on this topic, the assessment of the soil P availability still raise important questions. In addition to studies in which the efficiency of various extractants have been tested, such as Mehlich-1 and anion exchange resin, other techniques are being used for this purpose. Studies for evaluating the P distribution (dynamic) in different soil fractions and the changes in this fractions due to the management applied to crops and also the time of cultivation have been conducted with increasing intensity. Studies have also been carried out in order to identify the forms of P accumulation in soils. For this purpose, modern spectroscopic techniques such as spectroscopy based on synchrotron light source, have been used as a powerful tool, assisting in the identification of P compounds presents in the soil. The aims of this study were to evaluate the changes in available, fractions and forms of P in soils of Cerrado with different times under no-till cultivation system. Composite soil samples were collected in four areas under 5, 8, 12 and 18 years of no-till cultivation since the areas were opened, and also in a area under native vegetation. The soil in the area was classified as Typic Hapludox and the areas were cultivated alternating crops of soybeans, corn and cotton. Available P was extracted by Mehlich - 1 and anion exchange resin. The samples were subjected to Hedley´s chemical fractionation of P and X- ray absorption near edge structure (XANES). It was observed that, in general, the levels of P in the soil were always higher in cultivated areas, mainly in the topsoil, when compared to the area under native vegetation, which reflects the impact of phosphate fertilization. Surface application of phosphate fertilizer produced sharp gradients of P in the soil profile, especially for both labile and moderately labile fractions, and these fractions suffered the greatest influence of fertilizer compared to fractions of lower availability. Considering the same extractants, the organic P fractions contents were higher compared to the corresponding inorganic fractions. Forms of phosphorus in soils were predominantly associated with aluminum (Al) and iron (Fe), especially P associated with Al, and with Fe the association occurred predominantly through adsorption phenomenon rather than precipitation reactions.

Avloppsreningsverk är en spridningsväg för läkemedelsrester och per- och polyfluorerade alkylsubstanser (PFAS) till miljön. Genom en pågående revidering av avloppsdirektivet, vilket är ett genomförandedirektiv från EU, kommer det införas krav på reduktion av läkemedelssubstanser för att minska denna spridning. Kolonnförsök i bänkskala och pilotförsök i containerskala genomförs av Uppsala Vatten och Avfall AB och IVL Svenska Miljöinstitutet på Kungsängsverket i Uppsala för att testa tekniker för avskiljning av läkemedelsrester och andra mikroföroreningar. Syftet med detta examensarbete var att utvärdera de pågående försöken utifrån reningseffektivitet, kostnader, klimatpåverkan och utifrån de krav som kan komma att ställas i det reviderade avloppsdirektivet.  Avskiljningsgrad i avloppsvatten av perfluoroktansulfonsyra (PFOS), citalopram, diklofenak, metoprolol, oxazepam och summan av 14 svårnedbrytbara substanser vid singel- och seriedrift av granulerat aktivt kol (GAK) i kombination med efterföljande anjonbytare (AIX) undersöktes baserat på analysdata från provtagningar. För läkemedel sker reduktionen huvudsakligen med GAK. Efterföljande AIX bidrar med en kompletterande reduktion av diklofenak och PFOS. Vid byte av kol i GAK-filtret i kolonnförsöken påverkas reduktionen över efterföljande AIX, vilket syns genom desorption av diklofenak över AIX. Vid jämförelse mellan GAK-filtren i kolonnförsöken och GAK-filtren i pilotförsöken kunde liknande trender ses gällande hur snabbt avskiljningsgraden för olika substanser avtar vid ett ökat antal behandlade bäddvolymer (BV). Utvärdering av de substanser som ingår i förslaget till reviderat avloppsdirektiv utifrån de krav som ställs visade en genomsnittlig reduktion på över 80 % av sex utvalda substanser (amisulprid, citalopram, diklofenak, venlafaxin, ∑6&4-metylbenxotriazol and benzotriazol), och därmed uppfyllda reduktionskrav, fram till minst 24 000 behandlade BV i GAK-filtren och 60 300 behandlade BV i AIX-filtret. Av de undersökta teknikerna förväntas lägst kostnad och klimatpåverkan vid seriedrift av GAK i två steg om målet med reningen är att avskilja läkemedel. Om reningsmålet även inkluderar reduktion av PFOS förväntas lägst kostnad och klimatpåverkan vid seriedrift av GAK i två steg följt av AIX. / Wastewater treatment plants contribute to the spread of pharmaceuticals and per- and polyfluoroalkyl substances (PFAS) to the environment. The urban wastewater treatment directive from the European Union is under revision, and requirements for reduction of pharmaceutical substances will be introduced to reduce the spread. Column tests in bench scale, and pilot tests in a shipping container, are being conducted by Uppsala Vatten och Avfall AB and IVL Svenska Miljöinstitutet at Kungsängsverket in Uppsala with the aim of evaluating techniques to reduce pharmaceuticals and other micropollutants. This master thesis was aimed to evaluate the tests based on treatment efficiency, costs, climate impact and based on the requirements that may be set in the revised urban wastewater treatment directive.    Reduction of perfluorooctanesulfonic acid (PFOS), citalopram, diclofenac, metoprolol, oxazepam and the sum of 14 persistent pharmaceuticals in wastewater, with granulated activated carbon (GAC) in single- and two-stage series operation in combination with a following anion exchange resin (AE), were evaluated based on data from analyzed samples. The reduction of pharmaceuticals was mostly done by GAC. AE after GAC contribute with a complementary reduction of diclofenac and PFOS. When changing the resin in the GAC-filter in the column tests, the reduction over the subsequent AE-filter was affected, which could be seen by desorption of diclofenac from AE. A comparison between the GAC-filter in the column tests and the GAC-filter in the pilot test showed similar trends regarding how fast the treatment efficiency for different substances decreased with an increased number of treated bed volumes (BV). An evaluation of the substances that are included in the proposal to the revised directive showed an average reduction of six selected substances (amisulprid, citalopram, diclofenac, venlafaxine, ∑6&4-metylbenxotriazol and benzotriazol) over 80 % for 24 000 treated BV in the GAC-filter and 60 300 treated BV in the AE-filter. GAC in a two-step series operation was the technique with lowest expected cost and climate impact if the aim of the treatment was to reduce pharmaceuticals. If the aim of the treatment also includes reduction of PFOS, the lowest expected cost and climate impact was achieved with GAC in two-step series operation followed by AE.

Le son et la paille de blé, riches en hémicelluloses, sont deux co-produits de la récolte de blé, abondants et renouvelables, mais qui restent à mieux valoriser. Dans le but d'extraire ces hémicelluloses, possédant plusieurs propriétés intéressantes (filmogènes, épaississantes, émulsifiantes, stabilisantes…), un procédé de fractionnement a été élaboré. Ce procédé consiste, après extraction alcaline, en la purification des extraits hémicellulosiques obtenus. Deux techniques ont été appliquées : l'ultrafiltration et la chromatographie sur résine échangeuse d'anions. L'ultrafiltration a permis de concentrer les extraits d'hémicelluloses et de les purifier en éliminant dans le perméat la plupart des molécules contaminantes, essentiellement les sucres libres et les sels minéraux. Les principales limitations de cette étape étaient la viscosité des extraits et les phénomènes de polarisation de concentration et de colmatage des membranes. La percolation sur résine, quant à elle, a permis de décolorer les extraits et de produire des poudres d'hémicelluloses plus claires en fixant certaines molécules colorées telles que les molécules possédant des groupements phénoliques. La combinaison des deux techniques a permis de produire des hémicelluloses pures à 60%. L'extrapolation du procédé à l'échelle pilote par l'utilisation d'un extrudeur bi-vis a permis d'obtenir des poudres d'hémicelluloses pures à 40%. / Wheat bran and wheat straw are two by-products abundant and renewable, rich in hemicelluloses, but still not well valued. In order to extract these hemicelluloses characterized by their several interesting properties (film-forming, thickening, emulsifying, stabilizing…), a fractionation process was developed. This process consisted, after alkaline extraction, to purify the hemicellulosic extracts obtained. Two techniques were used: ultrafiltration and chromatography on anion exchange resin. The ultrafiltration allowed to concentrate the extracts and to purify them by removing in the permeate, the contaminating molecules, mostly free sugars and minerals. The main limiting factors of this stage were the extracts viscosity and the fouling of the membranes. The percolation on the resin discoloured the extracts and allowed to produce hemicellulosic powders with lighter colours and that by capturing the coloured compounds such as molecules with phenolic groups. The combination of the two techniques allowed the production of purified hemicelluloses; the purity was about 60%. The extrapolation of the process at a pilot scale using a twin-screw extruder allowed to obtain hemicelluloses with a purity of 40%.