O presente trabalho teve por objetivo avaliar a eficiência de remoção do surfactante aniônico alquilbenzeno linear sulfonado (LAS) em reator anaeróbio de leito granular expandido - EGSB (1,5 litros) com recirculação e alimentação com meio mineral. Além de caracterizar filogeneticamente a diversidade de bactérias na presença do surfactante. O sistema foi operado em condição mesofílica em 4 etapas: (I), (II) e (IV) com TDH de 32 horas, e (III) com TDH de 26 horas. Em todas as etapas a DQO foi em média de 609 \'+ OU -\' 137 mg/L e 14 \'+ OU -\' 1,71 mg/L de LAS afluente. As maiores remoções de LAS foram verificada nas etapas II e IV, com valores de 73,6 \'+ OU -\' 5,6% e 63,6 \'+ OU -\' 6,17%, respectivamente de. Na etapa III essa remoção foi de 47,8 \'+ OU -\' 6,2%. Por meio do balanço de massa constatou-se que 56,6% do total de LAS adicionado foram removidos compreendendo 48,4% por biodegradação e 8,2% por adsorção. A remoção de matéria orgânica não foi afetada com a adição do LAS e nem pela exposição prolongada a esse surfactante. Entretanto, a estrutura do grânulo foi comprometida quando da adição do surfactante, observado pelo aumento da concentração de sólidos totais efluente de 0,049 g/L na etapa I (sem LAS), 0,128 g/L na etapa II, 0,064 g/L na etapa III e 0,038 g/L na etapa IV, quando da adição de 14 \'+ OU -\' 1,71 mg LAS/L. Além disso, foi notada diminuição do diâmetro médio dos grânulos no decorrer da operação do reator de 0,36 cm nas etapas I e III para 0,34 cm na etapa IV. Por meio da técnica de tubos múltiplos (NMP) foi constatado aumento das bactérias anaeróbias totais e diminuição das arqueias metanogênicas, em função do tempo de operação do reator. As bactérias redutoras de ferro representaram 8% da biomassa anaeróbia na etapa IV. Por meio do seqüenciamento da região 16S do RNAr para o domínio Bacteria da biomassa da extremidade superior do reator e da biomassa do leito, foi verificado semelhança com os seguintes filos Proteobacteria, Firmicutes e Synergistetes. Notou-se diferença significativa entre as bibliotecas de clones para essas duas amostras. / This study aimed to evaluate the efficiency of removal of linear alkylbenzene sulfonate (LAS) in expanded bed reactor (1.5 liters) using granular sludge (EGSB) with recirculation and feed with mineral medium modified. The system was operated at mesophilic condition in four stages: (I) (II) and (IV) with HRT of 32 hours, and (III) with HRT of 26 hours. At all stages the COD averaged 609 \'+ OR -\' 137 mg/L and 14 \'+ OR -\' 1.71 mg/L LAS influent. The higher removals of LAS were found in stages II and IV, respectively, 73.6 \'+ OR -\' 5.6% and 63.6 \'+ OR -\' 6.17%. In stage III this removal was 47.8 \'+ OR -\' 6.2%. Through mass balance was found that 56.6% of total LAS added were removed by biodegradation comprising 48.4% and 8.2% by adsorption. The organic matter removal was not affected by the addition of LAS and not by prolonged exposure to this surfactant. However, the granule structure was compromised after the addition of surfactant, the observed increase in effluent total solids concentration of 0.049 g/L in stage I (no LAS), 0.128 g/L in stage II, 0.064 g/L in stage III and 0.038 g/L in stage IV when adding 14 \'+ OR -\' 1.71 mg/L. Furthermore, it was noticed significant decrease in mean diameter of the granules during the operation of the reactor of 0.36 cm in stages I and III to 0.34 cm in stage IV. Through the multiple tube method (MPN) was found to increase the total anaerobic bacteria and methanogenic archaea decreased depending on the time of reactor operation. Iron-reducing bacteria accounted for 8% of anaerobic bacteria total in step IV. By sequencing the 16S rRNA for the domain Bacteria biomass from the upper end of the reactor and the biomass of the bed, was found similar to the following phyla Proteobacteria, Firmicutes and Synergistetes. Significant difference was noted between the clone libraries for these two samples.

Orientador: Flavia Maria Netto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-19T21:19:52Z (GMT). No. of bitstreams: 1 Silva_FernandaGuimaraesDrummonde_M.pdf: 1363127 bytes, checksum: 68b1a97c95798f4425019ee900814160 (MD5) Previous issue date: 2012 / Resumo: Existem evidências numerosas sobre o papel dos radicais livres em uma série de condições patológicas, incluindo envelhecimento, câncer, esclerose múltipla, doenças cardiovasculares. Hidrolisados protéicos de diferentes fontes têm sido estudados por seu potencial antioxidante. A atuação antioxidante da proteína, na maioria das vezes, encontra-se limitada devido à conformação espacial, que concentra resíduos capazes de neutralizar radicais livres no interior da molécula, dificultando o acesso das espécies reativas aos centros nucleofílicos. A hidrólise da proteína contribui para aumentar a exposição desses resíduos de aminoácidos, aumentando sua atuação como antioxidante. Compostos fenólicos podem estar presentes em hidrolisados proteicos de origem vegetal, devido a sua associação com as proteínas. Métodos in vitro que simulam as condições do trato gastrointestinal permitem estudar como a digestão pode interferir na atividade antioxidante de peptídeos e compostos fenólicos. O presente trabalho tem como objetivos obter hidrolisados proteicos com capacidade antioxidante a partir da farinha de linhaça e avaliar o efeito da digestão in vitro pode interferir nessa atividade. A farinha de linhaça marrom foi desengordurada, obtendo-se a farinha de linhaça marrom desengordurada (FLMD). O concentrado proteico de linhaça (CPL) foi obtido a partir da FLMD por extração alcalina e precipitação no ponto isoelétrico seguida de neutralização. Para obtenção dos hidrolisados proteicos (HPL), a partir do CPL, com Alcalase, foi realizado um delineamento composto central rotacional (DCCR) 2². As variáveis independentes foram pH que variou entre 7,5 a 9,5 e relação enzima: substrato (E:S) que variou de 1:150 a 1:30. As variáveis dependentes foram grau de hidrólise (GH), teor de substâncias redutoras do reagente de Folin-Ciocalteau e atividade antioxidante, determinada por FRAP e ORAC. Teor de substâncias redutoras e atividade antioxidante foram avaliados a partir dos extratos aquosos e metanólico (metanol 70%). Os hidrolisados de maior atividade antioxidante, a FLMD e o CPL foram submetidos à digestão in vitro, simulando as condições da digestão gastrintestinal. As amostras antes e após a digestão in vitro foram caracterizadas por eletroforese em sistema SDS-PAGE Tricina e por cromatografia liquida de alta eficiência de fase reversa (HPLC- RP). O teor de substâncias redutoras e da atividade antioxidante das amostras FLMD, CPL e HPL foram avaliados antes e após a digestão in vitro. As condições ótimas para obtenção de HPL de maior GH (21,0%) são pH entre 7,5 e 8,0 e E:S entre 1:60 e 1:30, indicando que a faixa de pH ótimo da enzima e a alta E:S favorecem maior hidrólise do CPL. Para obtenção de HPL com maior teor de substâncias redutoras para os extratos aquoso (24 mg EAG/ g HPL) e metanólico (20 mg EAG/ g HPL) as condições ótimas são pH ~ 8,5 /E:S 1:30. Este resultado parece estar relacionado à liberação de compostos fenólicos ligados a proteína e também de peptídeos durante a hidrólise. Açúcares e aminoácidos aromáticos presentes no hidrolisado podem interferir na reação e superestimar o teor de fenóis dos HPL. A maior atividade antioxidante determinada pelo método de FRAP para o extrato aquoso (42 mg SF/ g HPL) se dá nas condições de pH ~ 9,5/E:S ~1:150 e para o extrato metanólico (40 mg SF/ g HPL) pH entre 8,5 e 9,0/E:S entre 1:90 a 1:150. Para o método de ORAC, as condições ótimas para maior atividade antioxidante no extrato aquoso (300 µmol TE/ g HPL) são pH entre 7,5 a 9,5/E:S ~ 1:30 ou ~1:150 e para o extrato metanólico (330 µmol TE/ g HPL) são pH ~ 8,5/E:S entre 1:150 e 1:30. Os hidrolisados de maior atividade antioxidante foram os obtidos em pH 8,5/E:S 1:90, e em pH 9,2/E:S 1:133 denominados HPL 0 e HPL 3, respectivamente. Para a FLMD, CPL e os hidrolisados, após a digestão in vitro, observou-se que o teor de substâncias redutoras totais aumentou (9 a 20 vezes) para todas as amostras. O teor de substâncias redutoras do CPL (~24 mg EAG/ g amostra), em ambos os extratos, após a digestão in vitro se igualou ao teor dos hidrolisados (~23 mg EAG/ g amostra). Este resultado sugere que tanto a hidrólise com Alcalase quanto o processo digestório liberam compostos redutores, dentre eles fenólicos da proteína de linhaça. A atividade antioxidante dos extratos de FLMD e CPL, determinada por FRAP, também aumentou (de 3 a 10 vezes) após a digestão, mas não se igualou à atividade antioxidante dos hidrolisados (48 mg SF/g amostra). No entanto, o CPL apresentou atividade antioxidante determinada por ORAC semelhante à dos hidrolisados no extrato aquoso (~420,24 µmol TE/ g amostra) e 10 % maior que o encontrado para os hidrolisados (~365 µmol TE/ g amostra) no extrato metanólico. Após a digestão in vitro, os hidrolisados apresentaram a maior atividade antioxidante medida por FRAP (50 mg SF/ g amostra), e o CPL, a maior atividade determinada pelo método de ORAC (~430 µmol TE/ g amostra). Estes resultados sugerem o processo digestório é tão ou mais eficiente que a Alcalase em liberar os compostos com atividade redutora no CPL. Uma vez que a metodologia de determinação da atividade antioxidante por ORAC tem maior proximidade com o mecanismo de oxirredução que ocorre in vivo, esses resultados sugerem o uso do CPL como melhor produto protéico da linhaça com maior potencial antioxidante para a formulação de nutracêuticos e alimentos funcionais / Abstract: There are several evidences which indicate the role of free radicals on a series of pathological conditions, including aging, cancer, multiple sclerosis and cardiovascular disease. Hydrolysates from different sources have been studied because of their antioxidant potential. The antioxidant activity of the protein, in most cases, is limited due to their conformation, which concentrates residues capable of neutralize free radicals in the molecule¿s core, hampering the access of the reactive species to nucleophilic sites. The protein hydrolysis contributes to increasing the exposure of these amino acid residues, increasing their role as antioxidants. Phenolic compounds may also be present in vegetable protein hydrolysates because of their association with proteins. In vitro methods that simulate the conditions of the gastrointestinal digestion are an important way to evaluate how the digestion affects the antioxidant activity of phenolic compounds and peptides. This study aims at obtaining hydrolysates with antioxidant capacity from defatted flaxseed flour and evaluate the effect of the in vitro digestion on this activity. The brown flaxseed flour was defatted, resulting in the brown defatted flaxseed meal (BDFM). The flaxseed protein concentrate (FPC) was obtained from the BDFM by alkaline extraction and precipitation at the isoelectric point followed by neutralization. To obtain the flaxseed protein hydrolysates (FPL), using FPC and Alcalase, a central composite rotational design (DCCR) was performed. The independent variables were pH ranging from 7.5 to 9.5 and enzyme: substrate ratio (E: S) that ranged from 1:150 to 1:30. The dependent variables were the degree of hydrolysis (DH), total phenolic content and antioxidant activity, determined by FRAP and ORAC. Phenolic and antioxidant activity were evaluated from the aqueous and methanol (70% methanol). The hydrolysates with the highest antioxidant activity, the CPL FLMD were submitted to the in vitro digestion. The samples obtained before and after the in vitro digestion were characterized by electrophoresis SDS-PAGE- tricine and HPLC. The total phenolic content and antioxidant activity of FLMD, CPL and HPL were evaluated before and after in vitro digestion. The optimum conditions to obtain HPL with the highest GDH (21.0%) are pH (7.5-8) and E:S ratio (1:60-1:30), which indicates that the Alcalase optimum pH and highest E:S ratio collaborates to highest hydrolysis of CPL. To obtain HPL with higher content of Folin-Ciocalteau reducing compounds content in aqueous (EAG 24 mg / g HPL) and methanol (20 mg EAG / g HPL) extracts, the optimum conditions were pH ~ 8.5 / E: S 1:30. This result seems to be related to the release of phenolic compounds bound to protein and also of peptides during hydrolysis. The highest antioxidant activity determined by the FRAP method in the aqueous extract (42 mg SF / g HPL) occurs under pH ~ 9.5 / E: S ~ 1:150 and the methanol extract (40 mg SF / g HPL) pH 8.5-9.0 / E: S 1:90-1:150. For the ORAC method, optimum conditions for increased antioxidant activity in aqueous extract (300 µmol TE / g HPL) are pH 7.5-9.5 / E: S ~ 1:30 or 1:150 and the methanol extract (330 µmol TE / g HPL) are pH ~ 8.5 / E: S 1:30-1:150. The hydrolysates with the highest antioxidant activities were obtained at pH 8.5 / E: S 1:90, and at pH 9.2 / E: S 1:133 denominated HPL ) and HPL 3, respectively. For FLMD, CPL and hydrolysates, after in vitro digestion, the content increased (9-20 times) for all samples. The Folin-Ciocalteau reducing capacity of the CPL (EAG ~ 24 mg / g sample) in both extracts after in vitro digestion equaled the content of hydrolysates (EAG ~ 23 mg / g sample). This result suggests that both hydrolysis with Alcalase and the digestion process are able to release phenolic compounds from the flaxseed products. The antioxidant activity of extracts of FLMD, CPL determined by FRAP, also increased (from 3 to 10 times) after digestion, but did not reached the antioxidant activity of hydrolysates (48 mg SF / g sample). However, when the activity was determined by ORAC, the FPC showed value similar to the hydrolysates, measured on the aqueous extract (~ 420.24 µmol TE / g sample) and 10% higher than on the methanol extract (~ 365 µmol TE / g sample). After in vitro digestion, hydrolysates showed the highest antioxidant activity measured by FRAP (SF 50 mg / g sample), and the FPC, the highest activity determined by ORAC method (~ 430 micromol TE / g sample). These results suggest that digestive process are equally or more effective than Alcalase in releasing peptides and phenolic compounds present in the FPC. Since the methodology for determining the antioxidant activity by ORAC utilizes a biologically relevant radical source, these results suggest the use of FPC as the best protein product of flaxseed with potential antioxidant in the formulation of nutraceuticals and functional foods / Mestrado / Nutrição Experimental e Aplicada à Tecnologia de Alimentos / Mestre em Alimentos e Nutrição

Pour réaliser des simulations précises aux temps longs pour des vagues non linéaires, il faut faire appel à des algorithmes d’évolution temporelle précis. En particulier, la combinaison d’un pas de temps adaptatif avec un facteur intégrant est connue pour être très efficace. Nous proposons une modification de cette technique. Le principe consiste à soustraire un certain polynôme à une EDP. Puis, comme pour le facteur intégrant, nous faisons un changement de variable pour retirer la partie linéaire. Mais nous espérons retirer quelque chose de plus afin de rendre l’EDP moins raide pour les calculs numériques. Le polynôme choisi est une expansion de Taylor autour du temps initial de la solution. Afin de calculer les différentes dérivées nécessaires, nous utilisons le Dense Output qui donne la possibilité d’approximer les dérivées de la solution à tout temps. Une fois le facteur intégrant modifié appliqué, nous faisons appel à une avance temporelle classique afin de résoudre l’équation d’évolution. Il a été considéré plusieurs schémas de Runge-Kutta avec pas de temps adaptatif. Nous avons tiré avantage des méthodes emboîtées, afin de ne pas calculer de nouvelles fonctions et perdre du temps de calcul, en utilisant uniquement des données déjà calculées durant l’évolution temporelle. Les résultats numériques montrent que l’efficacité de notre méthode varie selon les cas. Par exemple, nous avons vérifié que plus le profil de l’onde est pentue, plus notre méthode est efficace. Pour le modèle de vagues non linéaires le plus compliqué à notre disposition, le modèle HOS, nous avons pu réduire le nombre de pas de temps de calcul jusqu’à près de 30 % avec un schéma de Runge-Kutta de Dormand-Prince et jusqu’à plus de 99 % pour un schéma de Bogacki-Shampine. / Efficient time stepping algorithms are crucial for accurate long time simulations of nonlinear waves. In particular, adaptive time stepping combined with an integrating factor are known to be very effective. We propose a modification of the existing technique. The trick consists in subtracting a certain-order polynomial to a PDE. Then, like for the integrating factor, a change of variables is performed to remove the linear part. But, here, we hope to remove something more to make the PDE less stiff to numerical resolution. The polynomial is chosen as a Taylor expansion around the initial time of the solution. In order to calculate the different derivatives, we use a dense output which gives a possibility to approximate the derivatives of the solution at any time. The modified integrating factor being applied, a classical time-stepping method can be used to solve the remaining equation. We focus on various Runge-Kutta schemes with a varying step size. We take advantage of embedded methods and use an evolved adaptive step control. We do not need to calculate new functions and loose time of calculation only by using already estimated values during the temporal evolution. Numerical tests show that the actual efficiency of the method varies along cases. For example, we verified that steeper waves profiles give rise to better behaviour of the method. For fully nonlinear water wave simulations with the HOS model, we can save up to 30% of total time steps with a Dormand-Prince Runge-Kutta scheme and we can save up to 99% with the Bogacki-Shampine scheme.

Bullerskyddsskärmar används för att reducera buller från väg- och spårtrafik. Syftet med examensarbetet var att utvärdera standard EN 1793–6:2012, en mätmetod för att undersöka bullerskyddsskärmars effektivitet in-situ med avseende på ljudisoleringen. I nuläget bestäms bullerskyddsskärmars effektivitet med laborationsmätningar i ett diffust ljudfält, som inte överensstämmer med det direkta ljudfält och den komplexitet som är in-situ. Till följd av det blir ofta laborationsmätningarna missvisande. Det finns även en okunskap kring håligheter/ läckage och hur det påverkar den akustiska prestandan, vilket gör att det emellanåt leder till brister i installationen av bullerskyddsskärmar och att enhetens ljudreducering inte stämmer överens med förväntningarna. Det finns således ett behov av att bestämma en bullerskyddsskärms befintliga prestanda in-situ för att säkerställa de krav som ställs i specifikationerna. EN 1793–6:2012 ansågs vara lämplig för ändamålet men fler mätningar behövs utföras för att kunna säkerställa resultaten och för att verifiera mätsystemet. Ljudisoleringen bestämdes som en funktion av frekvenser i tersband och var giltiga i frekvensområdet mellan 200 Hz till 5 kHz respektive 400 Hz till 5 kHz. De undersökta bullerskyddsskärmar var: en i laminerat och härdat glas med aluminiumpelare, en icke-homogen vegetationsskärm i stålram och en kombinerad bullerskyddsskärm i akrylglas med aluminiumprofiler. Resultaten jämfördes med laborationsmätningar och/eller simuleringar i Insul. Bullerskyddsskärmarna i glas gav högre värden på ljudisoleringen än i laborationsmätning, ett resultat som kan bero på skillnaderna mellan diffust ljudfält och direkt ljudfält. Komplexiteten i vegetationsskärmen gjorde resultaten svåra att analysera, men läckage förekom i de högre frekvenserna. Adrienne-fönstren behövde bli specifikt beräknade för samtliga impulssvar eftersom dimensionerna för bullerskyddsskärmarna inte överensstämde med vad som definieras i EN 1793–6:2012 för certifieringsändamål. I EN 1793–6:2012 omnämns inte heller markreflektion, som påverkar den filtrerade signalen. Vidare studier behövs för att filtrera bort dessa oönskade komponenter. / Road traffic noise devices, for example noise barriers, are used to reduce the noise from road traffic and trams. The purpose of this master thesis is to evaluate the standard EN 1793-6:2012, a test method for determining noise barriers efficiency in-situ. Currently, noise barriers efficiency is determined with laboratory measurements in a diffuse sound field, which does not reflect the direct sound field and the complexity that are in-situ. As a result, laboratory measurements are often misleading. Due to a lack of knowledge about leakage, there are sometimes defects caused in the installation of the noise barriers that adversely affect the acoustic properties. There is thus a need to determine the intrinsic parameters of a noise barrier in-situ to ensure the requirements set in the specifications. The new method described in EN 1793-6:2012 was considered useful for the purpose but it was found that more measurements need to be performed to ensure results and to verify the measurement system. The sound insulation was determined for three noise barriers where results are expressed as a function of frequency in one third octave band and were valid in the frequency range between 200 Hz to 5 kHz respective 400 Hz to 5 kHz. The noise barriers tested were: a barrier in laminated glass with metal posts, a non-homogeneous vegetation barrier in a steel frame and a combined barrier with acrylic glass and metal. The results were compared with laboratory measurements and/or simulations in Insul. The glass barriers showed higher values ​​of the sound insulation index than the laboratory measurements, perhaps due to the different sound fields. The complexity of the vegetation barrier made the results difficult to analyze, but leakage occurred in the higher frequencies. The Adrienne temporal windows were specifically calculated for all impulse responses, since the dimensions of the noise barriers differed from the one defined in EN 1793-6: 2012 for certification purposes. Also, in EN 1793-6: 2012, ground reflection, which affects the filtered signal, is not mentioned. Further studies are needed to filter out these unwanted components.

Abstract Most of the steel produced in the world is based on the integrated blast furnace-converter route, which is based on the use of virgin raw materials. Large amounts of fossil-based, carbon containing reductants are used in blast furnaces, which results in carbon dioxide emissions into the atmosphere. Fossil carbon dioxide emissions from steel production can be reduced by new technologies or moving from non-renewable to renewable energy sources. Biomass-based reductants could be one way to reduce the specific emissions from blast furnace-based steel production. The aim of this thesis was to examine the techno-economic and CO₂ mitigation potentials of using bioreducers in blast furnace ironmaking. Bioreducer feasibility was analyzed in the Finnish context, but the research methods used can be applied more widely. The metallurgical properties of bioreducers were evaluated and compared to fossil-based reductants. The impact of bioreducers on blast furnace behavior and on other steel plant processes was evaluated, with an emphasis on the reductions achieved in CO₂ emissions at the plant scale. The CO₂ emissions, energy consumption and production costs of bioreducers were evaluated, as was the availability of energy wood for bioreducer production. The results show that solid, liquid and gaseous bioreducers can be produced with thermochemical conversion technologies. However, their suitability for blast furnace use varies greatly. The highest substitution of fossil-based reductants in a blast furnace is achieved with charcoal injection. The carbon footprint of torrefied wood, charcoal and Bio-SNG is moderate compared to fossil-based reducing agents and their production is energetically feasible. The economic feasibility of bioreducers is currently weak in comparison to fossil-based reducing agents, but competitive when compared to other CO₂ emission reduction measures such as carbon capture and storage. The biomass availability assessment revealed that sufficient amount of energy wood could be available for bioreducer production in the areas where Finnish steel plants are situated. The feasibility of bioreducer production could be improved by producing a number of products from the biomass and taking advantage of the process of integration possibilities. / Tiivistelmä Suurin osa maailmassa tuotetusta teräksestä valmistetaan integroidulla masuuni-konvertteri reitillä, joka perustuu neitseellisten raaka-aineiden käyttöön. Masuuniprosessissa käytetään suuri määrä fossiilisia, lähinnä hiilipohjaisia pelkistimiä, jotka aiheuttavat hiilidioksidipäästöjä ilmakehään. Fossiilisia hiilidioksidipäästöjä voidaan teräksenvalmistuksessa vähentää uusilla teknologioilla tai siirtymällä uusiutumattomista energialähteistä uusiutuviin. Biomassasta valmistetut pelkistimet voisivat olla yksi mahdollinen keino alentaa masuunipohjaisen teräksenvalmistuksen ominaispäästöjä. Tämän työn tavoitteena oli tarkastella biopelkistimien käytön teknistaloudellista potentiaalia masuunikäytössä ja aikaansaatavia hiilidioksidipäästövähenemiä eri systeemirajauksilla. Työssä keskityttiin tarkastelemaan biopelkistimien hyödynnettävyyttä lähinnä Suomen tasolla, vaikka käytetyt tutkimusmetodit ovat sovellettavissa myös laajemmin. Työssä arvioitiin biopelkistimien metallurgisia ominaisuuksia, niiden vaikutusta masuuniprosessiin ja laajemmin muihin terästehtaan prosesseihin, pääpainon ollessa saavutettavan CO₂ päästövähenemän tarkastelussa. Työssä tarkasteltiin biopelkistimien valmistuksen CO₂ päästöjä, energiankulutusta ja tuotantokustannuksia sekä energiapuun saatavuutta biopelkistimien tuotantoon. Tulokset osoittavat, että biomassasta voidaan valmistaa kiinteitä, nestemäisiä ja kaasumaisia pelkistimiä termokemiallisilla konversioteknologioilla, joiden soveltuvuus masuunikäyttöön vaihtelee suuresti. Masuuniprosessissa suurin fossiilisten pelkistimien korvaavuus saavutetaan käyttämällä puuhiili-injektiota. Torrefioidun puun, puuhiilen ja Bio-SNG:n hiilijalanjälki on varsin maltillinen verrattuna fossiilisiin pelkistimiin ja niiden tuotanto on energeettisesti järkevää. Biopelkistimien taloudellinen kannattavuus verrattuna fossiilisiin pelkistimiin on tällä hetkellä heikko, mutta kilpailukykyinen verrattuna muihin CO₂ päästöjen vähennyskeinoihin, kuten hiilidioksidin talteenottoon ja -varastointiin. Energiapuun saatavuus biopelkistimien valmistukseen on suurin alueilla, jotka sijaitsevat lähellä Suomen terästehtaita. Biopelkistimien tuotannon kannattavuutta voitaisiin parantaa tuottamalla useita tuotteita ja hyödyntämällä prosessi-integraatiota.

Carbon dioxide emissions to the atmosphere today cause problems around the world. In Sweden, the steel production contributes significantly to carbon dioxide emissions. The steel industry challenge is to improve the metallurgical processes to decrease the carbon dioxide emissions. One way to reduce the emissions is to use renewable carbon sources. The blast furnace process is a counter current reduction process for ironmaking. Raw materials such as iron ore agglomerates, coke and slag formers are charged at the top of the furnace while oxygen-rich blast air and powdered coal are injected in the bottom. The gases produced by combustion rise through the burden on the top of the furnace. The combustion of carbon produces carbon monoxide which is the reducing gas used for the reduction of iron oxides to pig iron. The process is the highest producer of CO2 emissions in Sweden; biomass can partially replace fossil carbon in coal blends for cokemaking, coal powder for coal injection and coke in self-reducing briquettes.  The purpose of this project was to maximize the addition of biomass in coal blends for cokemaking and the addition in briquettes produced for the recovery of iron bearing rest products. The challenge with biomass in cokemaking is its low density and high reactivity which decrease the coke yield and coke strength at the same time that it increases the coke reactivity. The coke quality has to be kept at sufficient quality in order to avoid effects on productivity and process stability in the blast furnace. The addition of biomass in briquettes is limited due to the low density of the biomass which may affect the strength of the briquettes. The effect of the addition of sawdust in coke and briquettes has been studied to understand the effect on reaction behaviour of bio-coal. Heat-treatment of sawdust with high volatile coal was performed in order to achieve a coating of coal on the sawdust surface and get less reactive sawdust. Torrefied sawdust contained 23 wt. % fixed carbon while the pre-treatment of sawdust with high volatile coal increased the content to about 60 wt. %. Pre-treated sawdust was added to coal blend for coke making and briquettes containing iron oxide. The pre-treated sawdust was added to five coal blends for coke production, the contents were 5, 10 and 20 wt. %, and a base blend was used as reference. Coke reactivity, chemical composition and cold compression strength in coke were studied. This work resulted in an improved bulk density; up to 20 wt. % pre-treated sawdust could be added to the coal blend and still keep a bulk density of 800 kg/m3. The coke yields in cokes with pre-treated sawdust were comparable to the coke reference. The temperature at which carbon in coke began to be consumed was slightly higher in coke containing sawdust treated with 50 wt. % high volatile coal. It was estimated that the CO2 emission from fossil coal could be reduced with 8.6 % per ton hot metal (THM) with the addition of 10 wt. % pre-treated sawdust to coal blends for cokemaking. The addition of 20 wt. % pre-treated sawdust could reduce the CO2 emission with 10% per THM. In addition, two different mixes of briquettes were produced, one with torrefied sawdust and one with pre-treated sawdust. The chemical composition and reduction of iron oxides in briquettes was also studied and evaluated. Briquettes with treated sawdust were more compact, i.e. had a higher density than briquettes containing torrefied sawdust. The amount of hematite that could be added to the briquette mixes was 0.107 moles in briquettes with torrefied sawdust and 0.112 moles in briquettes with pre-treated torrefied sawdust. / Koldioxidutsläppet till atmosfären orsakar idag problem runt om i världen. I Sverige bidrar stålproduktionen avsevärt till koldioxidutsläppet. Stålindustrin har som en utmaning att förbättra de metallurgiska processerna för att sänka utsläppet av koldioxid. Ett sätt att sänka koldioxidutsläppen är att minska påverkan genom att använda förnybara kolkällor. Masugnsprocessen är en kontinuerlig reduktionsprocess för råjärnframställning och en av processerna där det används reduktionsmedel från fossila kolkällor. Råmaterial som järnmalm, koks och slaggformare chargeras på toppen av ugnen medan syrgasberikad blästerluft och pulveriserat kol injiceras i botten av ugnen genom masugnens formor. De gaser som produceras vid förbränning stiger upp genom beskickningen upp till ugnens topp. Vid förgasning av kol bildas kolmonoxid som är den reducerande gasen, den möjliggör reduktionen av järnoxider vid framställning av råjärn. Torrefierad biomassa kan delvis ersätta fossilt kol i kolblandningarna för kokstillverkning, i kolinjektionen och i briketter. Syftet med detta projekt var att maximera mängden tillsatt biomassa i kolblandningarna för kokstillverkning och i briketter för återvinning av järnbärande restprodukter. Utmaningen med biomassa i kokstillverkningen är den höga reaktiviteten och den låga densiteten av kol, vilket resulterar i låg koksutbyte när den tillsätts i kolblandningar. Biomassa innehåller också en högt halt flyktiga ämnen vilket resulterar i koks med låg hållfasthet och hög reaktivitet. Kokskvalitén måste behållas för att undvika processvariationer i masugnen. Tillsatsen av biomassa i briketter, är begränsat då biomassa kan påverka briketternas hållfasthet. Effekten av tillsatsen av biomassa i koks och briketter har studerats för att kunna förstå reaktionsbeteendet i dessa när torrefied sågspån och förbehandlat sågspån med hög fluiditetskol har tillsatts till blandningarna. Värmebehandling av torrifierat sågspån med en hög fluiditeteskol gjordes för att uppnå en mindre reaktiv biomassa. Torrifierat sågspån innehöll 22.9 viktsprocent kol, förbehandlingen av sågspån med hög fluiditetskol ökade halten till cirka 60 viktsprocent. Den behandlade sågspånen tillsattes till fem kolblandningar för koksframställning, 5, 10 och 20 viktprocent tillsattes till en bas blandning som användes referens. Koksreaktiviteten, kemisk sammansättning och hållfasthet i koks studerades. Arbetet resulterade i en förbättrad bulkdensitet då upp till 20 viktprocent förbehandlad biomassa kunde tillsättas i kolblandningen och fortfarande behålla en bulkdensitet på 800 kg/m3. Koksutbytet i alla koks med förbehandlat sågspån var jämförbart med koksreferensen. Temperaturen där kemisk kol i koks började förbrukas, var något högre i koks som innehöll sågspån med 50 viktsprocent hög fluiditetskol. Koldioxidutsläppen från fossilt kol per ton råjärn (THM) uppskattades att vara 8,6 % lägre med tillsatsen av 10 viktprocent förbehandlat sågspån i kolblandningar för kokstillverkning. Tillsatsen av 20 viktprocent skulle innebära en minskning på 10 % per ton råjärn. Briketter med två olika blandningar framställdes, en blandning med torrifierat sågspån och en blandning med behandlat sågspån. Briketterna karakteriserades genom att analysera den kemiska sammansättningen och reduktionen av järnoxider i termisk reducerade briketter. Briketter med behandlat sågspån var mer kompakta, d.v.s. hade en högre densitet än briketter som innehöll torrifierad sågspån. Mängden hematit som kunde tillsättas i mixen med torrifierad sågspån var 0.107 mol, medan i mixen med förbehandlat sågspån 0.112 mol kunde tillsättas. / Bio4metals / CAMM

The aim of this thesis is to analyze and determine the actual flow of oil and natural gas in Europe, from the results to draw conslusions of the weight of the EU's dependence on Russian energy supplies and subsequently to determine the possibilities and prospects for further security flows of oil and natural gas to the EU. Oil and natural gas are the basic strategic raw materials of world economics, including economics of European countries. Most of the European countries does not have adequate supplies of energy raw materials. In particular, EU countries are therefore dependent on external supplies of oil and natural gas. The first chapter of the thesis is focused on oil and natural gas as major raw materials for the current energy situation in Europe. I defined the terms "oil" and "natural gas" and I analyzed the significant deposits of these materials and described their current production and consumption in Europe. In the second chapter I focused on the current flows of oil and natural gas in Europe, particularly on the European network of pipelines. On the baisis of these two chapters I specified the weight of the EU's dependence on energy supplies from Russia and identified the main problems of these supplies. In the third chapter of the thesis I dealt with the security flow of oil and natural gas to the EU and its perspectives and I gave the EU energy policy. I have analyzed selected documents of European energy policy, the EU's energy mix and I identified possible ways to reduce the EU's energy dependency. I included diversification of supply routes and the diversification of EU energy mix among these options. In conclusion, I summarized the current European energy situation, assessed European energy policy and outlined its future development.

[pt] A Corrosão Influenciada por Microrganismos (CIM) ou biocorrosão é reconhecida como um dos fenômenos causadores de inúmeros problemas nas indústrias de petróleo e gás, pois causa sérios danos ao material reduzindo sua vida útil. Neste trabalho foram avaliados os efeitos da biocorrosão caracterizado pela cinética de formação de biofilme em uma junta soldada longitudinal de aço API X80 obtida pelo processo de arco submerso (SAW). Durante o processo de soldagem forma-se uma região com características microestruturais distintas do metal de base e do metal de adição, denominada de zona termicamente afetada (ZTA). Assim essa zona poderá ter uma adesão microbiana diferenciada, visto que diferenças superficiais em um material, seja por natureza química ou física, podem limitar ou facilitar a adesão microbiológica. Por esse motivo foi realizado um estudo comparativo entre a cinética da formação de biofilme na junta soldada de um aço API X80. Também foi avaliada a influência das características físicas da superfície na adesão microbiana utilizando dois tipos de superfície: com a rugosidade original e polido com pasta de diamante com granulação de 6μm. Estas superfícies foram expostas ao fluido de processo (água do mar da Baía de Guanabara) em um sistema dinâmico. Foram realizadas tanto a quantificação microbiana, como também a quantificação dos ácidos orgânicos, sulfato depletado e ferro total para avaliar os nutrientes disponíveis e a bioatividade das reações bacterianas. A rugosidade superficial e o biofilme formado foram caracterizados morfologicamente e a sua presença correlacionada com a formação de pites. / [en] The Microbiologically Influenced Corrosion (MIC) or bio-corrosion is recognized as one of the phenomena that cause a lot of problems in petroleum and gas industries, because it causes serious damages to the materials, reducing its life cycle. This study evaluated the effects of bio-corrosion characterized by the biofilm formation kinetics in longitudinal welds of API 5L X80 steel obtained by the process of submerged arc welding (SAW). During the welding process a region with different microstructural characteristics of the base metal and weld metal is formed, called heat affected zone (HAZ). Thus this zone can have a differentiated microbial adhesion since the different surfaces of a material, either by chemical and physical nature, can limit or facilitate the microbial adhesion. For this reason a comparative study of biofilm formation kinetic on the welded joint was conducted. The influence of the physical characteristics of the surface in microbial adhesion was also evaluated using two kinds of surface: steel with real roughness and steel polished with diamond paste with grain size of 6 μm. These surfaces were exposed to the process fluid (Guanabara Bay seawater) in a dynamic flow system. The microbial quantification was held. Organic acids, depleted sulfate and total iron were also measured to evaluate the available nutrients bioactivity of bacterial reactions. Surface roughness and biofilm were characterized morphologically and correlated with pitting formation.

The thesis deals with one group of small fruits, the genus Ribes, ie currants, and gooseberries. It assesses their physical and chemical parameters with respect to the possibility of use in these properties for the design of a new type of product – beverages. Titration, spectrometric and other methods were used for the evaluation of these properties. A total of fifteen of these methods were available (total juice yield, juice pH, total dry matter, soluble fruit dry matter, titratable acidity, formolic number, reducing carbohydrate content, D-glucose, D-fructose and sucrose content, total polyphenolic substance content, anthocyanins, vitamin C and total antioxidant capacity) and a total of nine analytes (copper, iron, magnesium, phosphorus, zinc, manganese, potassium, calcium and sodium) were selected for the determination of mineral elements. For two years (harvest 2014 and 2015), these parameters were monitored for color variants of currants (white, red and black) and gooseberries (green-fruited, yellow-fruited and red-fruited). A total of six white varieties were tested in the group of currants - Olin, Jantar, Primus, Blanka, Viktoria and Orion, eleven varieties of red currants - Junnifer, Jesan, Detvan, Rovada, Rubigo, J.V.Tets, Tatran, Losan, Kozolupský raný, Stanca, NŠLS 11/6 and eleven varieties of black currant varieties - Ometa, Démon, Triton, Ben Hope, Ruben, Ben Gairm, Ben Lomond, Moravia, Ben Conan, Fokus and Ceres. A total of five varieties of green-fruited gooseberries were tested - Zebín, Mucurines, Rixanta, Rodnik and Prima. Yellow-fruited gooseberries were available in four varieties - Lemon Giant, Invicta, Golden Fig and Darek. The red-fruited gooseberries included varieties - Rolonda, Alan, Karat, Karmen, Krasnoslawjanskij, Himnomacki Rot, Remarka, Tamara and Black Neguš. Using Tukey's test, an analysis was performed and by scoring individual varieties based on the results of individual analyzes, a list of recommended varieties was compiled for further work on the development of a new beverage. Unfortunately, in 2015 there were very few fruits of green-fruited and yellow-fruited gooseberries, so it was decided that the volume of fruit will fall on the testing of bioactive substances. Therefore, at the end of the work, it is not possible to objectively evaluate these varieties of gooseberries in the whole range of analyzes. Therefore, the point evaluation of varieties was based on the averages of individual varieties. The red-fruited varieties were available in full, and therefore a full evaluation could take place. The most significant differences between red gooseberry varieties were in the content of bioactive substances (the content of polyphenolic substances, anthocyanin dyes, and vitamin C) and antioxidant capacity. These results were provided to the food subject, which continued to work with these values. Based on this project, utility model No. PUV 2016-33171 and the resulting combined drink based on wine and fruit juice were developed.

Diploma thesis is focused on the chemical analysis of the juices of black, red and white currant and jostaberry (Ribes a Ribes x culverwellii). The theoretical part is focused to the definition of fruit, fruit importance in human nutrition, description of Ribes and Ribes x culverwellii genuses, active substances in the currants and the jostaberry, description of selected chemical parameters and the determination of some of them. The procedures of determining for the following chemical parameters are described in the experimental section: determination of reducing sugars, determination of total and soluble solids, formol number, pH, titratable acidity, determination of total phenols and anthocyanins and determination of vitamin C in two samples jostaberry, six varieties of black currants, one variety of white currant and two varieties of red currants. Based on the evaluation of the obtained results, the comparison was made with different varieties and the thesis that "overall comparison of the different varieties in the content of phenolic compounds, vitamin C and anthocyanins appears to be the most promising variety of blackcurrant demon. It should however be noted that the highest content of phenolics and anthocyanins were determined in jostaberry„ has been suggested.