What kinetic and thermodynamic characteristics are established in a melt of hydrogen-reduced iron ore pellets? The pellets contain self-fluxing slag components which upon melting form an initial slag. Refining capabilities of this slag, such as dephosphorization power, are investigated in a lab-scale vertical furnace. Understanding the initial slag and the reactions taking place when hydrogen-reduced iron ore pellets melt is important for future optimization of ingoing raw materials as well as industry scale process design. A sample of either crushed hydrogen-reduced iron ore pellets or a powder mixture representative of iron ore pellets in terms of composition was melted in a lab-scale vertical furnace. The sample was lowered into the argon atmosphere furnace which had a temperature of 1600°. The sample was kept inside a magnesia crucible with a molybdenum loosely-fitted lid. The purpose of the lid was to fix the oxygen partial pressure. The reduction degree of the pellets or corresponding powder mixture as well as the total melting times were varied. XRF and OES analysis were employed to find the composition of the slag and metal phases, respectively. SEM analysis was employed to investigate phases present in the slag. Comparison of melted iron ore pellets and corresponding powder mixture show that powder can be employed to represent reduced iron ore pellets accurately. It was found that reduction degree strongly impacts both phosphorus and vanadium distributions as well as the types of phases formed in the slag fraction. During melting, almost all of the Vanadium and most of the Phosphorus content goes to the slag fraction. At lower reduction degrees, dephosphorization is greater; however, the Phosphorus content in the steel is still quite high at 130 ppm or higher. Modification to the amount and/or composition of the self-fluxing slag is suggested to reach lower levels of phosphorus in the steel. / Vilka kinetiska och termodynamiska egenskaper skapas i en smälta av vätgasreducerade järnmalmspellets? Pellets innehåller självflussande slaggkomponenter som vid smältning bildar en initial slagg. Slaggens raffineringsförmåga, till exempel fosforreningsförmåga, undersöks i laboratorieskala. För framtida optimering av ingående råvaror såväl som industriellskalig processdesign är det viktigt att förstå den initiala slaggen samt de reaktioner som äger rum vid nedsmältning av vätgasreducerade järnmalmspellets. Ett prov av antingen krossade vätgasreducerade järnmalmspellets eller en pulverblandning som är representativ för järnmalmspellets med avseende på sammansättning smältes ned i en laboratorieskalig vertikal ugn. Ugnen hade en argonatmosfär och temperatur på 1600°C då provet sänktes ner i ugnen för smältning. En magnesiumoxiddegel med ett löst inpassat molybdenlock användes som behållare för provet under nedsmältningen. Syftet med locket var att kontrollera syrgaspartialtrycket. Reduktionsgraden av pellets eller motsvarande pulverblandning såväl som de totala smältningstiderna varierades. XRF och OES mätverktyg användes för att undersöka sammansättning av slagg- och metallfraktionerna. SEM analys användes för att identifiera närvarande faser i slaggfraktionen. Jämförelse av nedsmälta vätgasreducerade järnmalmspellets med motsvarande pulverblandning visar att de två är representativa av varandra till stor grad. Resultaten visar på att reduktionsgraden påverkar starkt både fosfor- och vanadinfördelningarna samt faserna som bildas i slaggfraktionen. Vid smältning går nästan all mängd vanadin och majoriteten av fosfor till slaggfraktionen. Vid lägre reduktionsgrader är fosforreningen bättre. Fosforhalten i stålet är relativt hög och har ett värde på 130 ppm eller högre för samtliga prover. Ändring av mängden och/eller sammansättning av den självflussande slaggen rekommenderas för att nå lägre nivåer av fosfor i stålet.

In this doctoral dissertation, two laser-based sensors were evaluated for different applications. Laser Induced Incandescence (LII) is a technique which can provide nonintrusive quantitative measurement of soot and it provides a unique diagnostic tool to characterize engine performance. Since LII is linearly proportional to the soot volume fraction, it can provide in situ, real time measurement of soot volume fraction with high temporal and spatial resolution. LII has the capability to characterize soot formation during combustion. The soot volume fraction from both flames and a soot generator was investigated with LII. The effects of experimental parameters, such as laser fluence, gate delay, gate width and various laser beam focusing, on LII signal was studied. Laser Induced Breakdown Spectroscopy (LIBS), a diagnostic tool for in situ elemental analysis, has been evaluated for on-line, simultaneous, multi-species impurity monitoring in hydrogen. LIBS spectra with different impurity levels of nitrogen, argon, and oxygen were recorded and the intensity of the spectral lines of Ar, O, N, and H observed were used to form calibration plots for impurities in hydrogen measurements. An ungated detection method for LIBS has been developed and applied to equivalence ratio measurements of CH4/air and biofuel/air. LIBS has also been used to quantitatively analyze the composition of a slurry sample. The quenching effect of water in slurry samples causes low LIBS signal quality with poor sensitivity. Univariate and multivariate calibration was performed on LIBS spectra of dried slurry samples for elemental analysis of Mg, Si and Fe. Calibration results show that the dried slurry samples give good correlation between spectral intensity and elemental concentration.

The need for energy and fuels is predicted to grow within the next decades, in parallel to the need of decreasing the emissions to air and water to operate within the planetary boundaries. The alternatives to consider as energy or fuel options need to be environmentally friendly, evaluated over the whole life cycle. Hydrogen is one of the considered alternatives because it contains no carbon and has a good environmental performance when produced from renewable sources. It can be produced by a variety of methods, where electrolyzers have a good potential environmental impact if powered by renewable energy. Electrolyzers cleave water into hydrogen and oxygen, by using electricity and water. There are currently four technologies on the market or under development but there is a lack of LCA-studies that compare these. This study is an attributional LCA-study, evaluating the potential environmental performance of two electrolyzers: PEMEC and SOEC. The result from this study is thereafter compared to a parallel study of one other electrolyzer: Alkaline. The LCA study considers six impact categories: Abiotic Depletion (element), Abiotic Depletion (fossil), Acidification Potential, Eutrophication Potential, Global Warming Potential and Photochemical Ozone Creation Potential. The system boundary is set as cradle to gate. The electricity source for hydrogen production is evaluated in a sensitivity analysis, together with a scenario of future estimated developments. The electricity during hydrogen production has the highest impact of the life cycle for PEMEC and SOEC, where the energy source has a great impact on the result. PEMEC has the lowest potential environmental impact, in comparison to Alkaline and SOEC, which comes from low energy consumption and low weight of materials with high environmental impact. / Energi- och bränslebehovet förväntas öka inom de närmsta decennierna, samtidigt som utsläpp till luft och vatten måste minska för att nå uppsatta klimatmål. De alternativ som tas fram behöver vara miljövänliga, med bra klimatresultat sett över hela livscykeln. Vätgas är ett alternativ som övervägs, på grund av högt energiinnehåll och låga utsläpp till följd av att den är fri från kol. Vätgas kan produceras med en mängd metoder, där genom elektrolys anses vara en av de bästa teknikerna ur miljösynpunkt. En elektrolysör producerar vät- och syrgas genom att sönderdela vatten med hjälp av elektricitet. Det finns fyra elektrolys-varianter på marknaden och under utveckling, men det saknas LCA-studier där dessa jämförs mot varandra. Denna studie är en bokförings LCA av två elektrolyser: PEMEC och SOEC, som jämförs med resultatet från en parallell studie av en annan elektrolys-typ: Alkalisk. Potentiell miljöpåverkan mättes i sex stycken kategorier: resursutarmning (fossila resurser och ämnen), försurning, övergödning, global uppvärmning och fotokemiskt marknära ozon. Systemgränsen är satt från råmaterialutvinning till vätgasproduktion. Valet av elektricitetskälla för vätgasproduktion utvärderas i en känslighetsanalys, tillsammans med påverkan av framtida teknikers konstruktion. Livscykelfasen ”produktion av vätgas” har övervägande högst påverkan över livscykeln för SOEC och PEMEC, där elektriciteten är den bidragande faktorn. Elektrolysmodellen PEMEC har uppskattningsvis lägst miljömässig påverkan över livscykeln. Den låga påverkan för PEMEC kan härledas till låg elektricitetsförbrukning under vätgasproduktionen samt låga vikter av material med hög miljömässig påverkan.

In connection to the increase of emissions of greenhouse gases, electrification of the society is pointed out as absolute necessary to achieve the climate goals. To succeed with this, a substantial proportion of the intermittent electricity production needs, with the help from technical solutions, be used as a buffer for this production. The production of renewable hydrogen gas is seen as one of the solutions. The purpose of this study is to function as a foundation for a pilot study for establishment of production of renewable hydrogen which Jämtkraft will conduct during 2023. The study is compiled with information from updated science reports and studies, authorities or equate sources, Jämtkraft and workshops. The production cost of hydrogen gas has been set to price of electricity, three sizes of electrolysers and two types of electrolysers. The selling price has been divided into the transport sector and the industry sector. The calculations have been made with help from calculation methods from Jämtkraft and according to levelized cost of hydrogen formula. It is clear the production cost of hydrogen strongly correlates with the electricity price. The size of the electrolyser also affects, a larger electrolyser decreases the production costs of hydrogen. The difference between types of electrolysers do not affect the cost significantly, rather the placement and energy source to the hydrogen production. In comparison to 2020, the competitiveness for hydrogen within the transport sector has increased. The increase of the electricity cost has decreased the competitiveness within the industry sector. For economic success of an establishment of hydrogen production in Jämtland a careful analyse of customer interest must be made and an adjustment of selling price according to the electricity price. An investment rather towards the transport sector rather than the industry sector is to recommend. / I samband med de ökade utsläppen av växthusgaser, anses elektrifiering av samhället vara absolut nödvändigt för att uppnå klimatmålen. För att lyckas med detta, krävs det att en storandel av den intermittenta elproduktionen genom tekniska lösningar kan nyttjas som en buffert för denna produktion. Där ses produktion av förnyelsebar vätgas som en avlösningarna. Syftet med studien är att fungera som underlag för den förstudie för etableringav produktion av förnyelsebar vätgas som Jämtkraft genomför under 2023. Studien har sammanställts med information från uppdaterade forskningsstudier, myndigheter ellerl ikställda källor, Jämtkraft samt workshops. Vätgasproduktionskostanden har ställts mot elpris, tre storlekar på elektrolysör samt två typer av elektrolysör. Försäljningspriset har fördelats på transport-, och industrisektor. Beräkningarna har gjort med kalkylmetoder från Jämtkraft samt enligt Levelized Cost of Hydrogen- modellen. Det är tydligt är att vätgasproduktionskostanden korrelerar stark med elpriset. Även storleken på elektrolysör påverkar, en större elektrolysör minskar vätgasproduktionskostnaden. Typ av elektrolysör påverkar inte kostnaden nämnvärt, utan mer placering och vilken energityp som är källa till vätgasen. Sett mot 2020 har konkurrenskraften för vätgas inom transportsektorn ökat. Ökningen av elkostnaden, sett mot 2020, har bidragit till en minskad konkurrenskraft mot industrisektorn. För att ekonomiskt lyckas med en etablering av förnyelsebar vätgasproduktion i Jämtlands län måste en noggrann kundintressenanalys göras samt anpassa försäljningspriset efter elpriset. En satsning mot transportsektorn snarare än industrisektorn är att rekommendera. / <p>2023-08-22</p>

O objetivo deste trabalho foi enriquecer consórcio microbiano a partir de mistura de lodo granular de digestor anaeróbio de fluxo ascendente sob condições fototróficas anoxigênicas. Por meio de técnica de biologia molecular foi possível identificar 17 unidades taxonômicas operacionais (UTO) no consórcio microbiano, dentre as quais seqüências similares a Rhodobacter, gênero amplamente citado nos estudos de produção de gás hidrogênio por bactérias fototróficas. Exames microscópicos do consórcio fototrófico indicaram predomínio de bacilos Gram-negativos. Ensaios sob condições fototróficas foram realizados com dois meios de cultivo (RCVB e FANG) e os seguintes substratos orgânicos: ácido acético, butírico, cítrico, lático e málico, empregados como fonte de carbono, tanto para o crescimento celular, como para a produção do gás hidrogênio. A relação C/N inicial foi 30/4 e posteriormente 15/2, com o objetivo de favorecer o crescimento celular e a produção do \'H IND.2\'. A concentração dos substratos foi determinada de forma com que essa relação se mantivesse a mesma. O crescimento celular e consumo dos ácidos orgânicos foram similares para os dois meios de cultivo empregados. Entretanto, a produção do gás hidrogênio foi maior nos ensaios com o meio FANG. Dentre os substratos utilizados o consumo dos ácidos cítrico e málico foram os maiores (~100%), para concentrações iniciais de 3,3 g/L e 2,6 g/L, respectivamente. O menor consumo 25% foi observado em meio RCVB e ácido acético (2,5 g/L). O crescimento da biomassa variou de 0,06 g/L a 1,1 g/L, enquanto que a velocidade máxima específica de crescimento variou de 0,4 a 0,2 g SSV/L.d entre os substratos utilizados. A menor e maior concentração de hidrogênio foram de 8,5 e 22 mmol \'H IND.2\'/L, para os reatores alimentados com ácido lático e málico em meio FANG, respectivamente. Pôde-se concluir que o consórcio fototrófico enriquecido foi capaz de utilizar os ácidos orgânicos para produção do gás hidrogênio. / The aim of this work was enrich a mixture of granular sludge of an up flow anaerobic sludge blanket (UASB) under anoxygenic phototrophic conditions. The techniques of molecular biology identified 17 operational taxonomic units (UTO) in the microbial consortium among the sequences analised, which were similar to Rhodobacter, genus widely cited in studies of hydrogen gas production by phototrophic bacteria. Microscopic examinations of the phototrophic consortium showed predominance of Gram-negative bacilli. Tests were conducted under phototrophic conditions with two culture media (RCVB and FANG) and the following organic substrates: acetic, butyric, citric, lactic and malic acids that were used as carbon source for both cell growth and for the hydrogen gas production. The carbon nitrogen ratio (C/N) in the preliminaries tests was 30/4 and then it was changed to15/2 in order to improve the cell growth and hydrogen production. The concentration of substrates was determined for remain the same carbon/nitrogen ratio among the substrates. The cell growth and consumption of organic acids were similar for the two culture media used. However, the production of hydrogen gas was higher in trials with the medium FANG. Among the substrates used, the consumption of malic and citric acids were the highest (~100%) for initial concentrations of 3.3 g/L and 2.6 g/L, respectively. The shortest consumption (25%) was observed for the cells that grew on acetic acid, 2.5 g/L in RCVB culture medium. The growth of the biomass varied from 0.06 g/L to 1.1 g/L, whereas the maximum specific growth rate ranged from 0.4 to 0.2 g VSS/L.d between the substrates used. The lowest and highest concentrations of hydrogen were 8.5 and 22 mmol \'H IND.2\'/L for the reactor fed with lactic acid and malic acid in FANG\'s medium, respectively. It was concluded that the phototrophic consortium was able to use those organic acids for the production of hydrogen gas.

Le projet Cigéo, mené par l’ANDRA, vise à permettre à l’horizon 2030 le stockage géologique des déchets les plus radioactifs du parc nucléaire français. Ces déchets, qui seraient placés dans des alvéoles souterraines de plusieurs centaines de mètres, sont susceptibles de relâcher de l’hydrogène gazeux (H2), un gaz inflammable dans l’air lorsque sa concentration dépasse 4%. Pour la sécurité des installations, il est indispensable de s’assurer que la concentration de H2 dans les alvéoles de stockage reste inférieure à sa limite de dangerosité. L’objectif de cette thèse, menée à l’ONERA, est de concevoir et réaliser un Lidar permettant de profiler à distance la concentration de H2 (0-4%), sur plusieurs centaines de mètres, avec une forte résolution spatiale (< 3 m), et de proposer ainsi un moyen non intrusif de détection et de prévention du risque lié à l’hydrogène. Le principe retenu est celui d’un Lidar Raman vibrationnel dans le domaine ultra-violet (355 – 420 nm). Pour sa conception, nous avons pris en compte les conditions particulières prévues dans les alvéoles de stockage. Une chaine de détection très sensible à comptage de photons a été choisie et mise en oeuvre, basée sur des détecteurs SiPM (Silicium Photomultiplier). La nécessité d’employer une voie de mesure de la vapeur d’eau, simultanément à l’hydrogène, a été mise en évidence et est liée au recouvrement partiel des spectres de diffusion Raman de H2 et H2O. Un analyseur spectral à trois voies de mesure (H2, H2O, et N2 utilisé comme référence) a été conçu et mis en place. Une méthode de traitement de signal en temps réel a enfin été réalisée pour visualiser les profils de concentrations de H2 et H2O. L’ensemble du système lidar a pu être testé dans une scène de portée réduite (100 m) permettant des relâchements d’hydrogène. Des mesures simultanées de profils de vapeur d’eau naturelle et de dihydrogène (0-2%) ont pu être démontrées avec succès à 85 m, avec une résolution spatiale et temporelle de 1 mètre et 1 minute respectivement, pour une détectivité de 600 ppm. / The CIGEO project, led by the ANDRA agency, aims at enabling future deep geological disposal of french nuclear waste packages. Those packages could be stored in hundred-meters long underground galleries, and may release hydrogen gas (H2), which is explosive at concentrations above 4% in the air. For safety concerns, it is important to ensure that H2 concentration remains well below the lower explosive limit. The objective of this thesis work, conducted at the ONERA agency, is to design and build a lidar which enable high-resolution (3 m) remote profiling of H2 concentration (0-4%) over hundreds of meters. Such a lidar could perform nonintrusive H2 detection and then prevent H2-related explosion risks. This lidar measures vibrational Raman scattering in the UV domain (355 – 420 nm). Its design takes into account the specific conditions expected in storage galleries. A highspeed and sensitive detection stage has been chosen, based on SiPM (Silicium Photomultiplier) technology in photon counting mode. Due to a spectral overlap between molecular hydrogen and water vapor Raman spectra, the need of a H2O measurement channel has been demonstrated. A three-channel spectral analyzer (H2, H2O and N2 used as reference) has been designed and implemented. Signal processing in real time has been developed to display H2 and H2O concentration profiles. This lidar has been tested in a reduced range scene (100 m) enabling hydrogen gas releases. Simultaneous measurements of concentration profiles of natural water vapor and hydrogen gas (0-2%) have been performed at 85 m with 1-meter and 1-minute resolution and a 600 ppm detectivity.

Supramolecular chemistry has asserted itself as a significant multidisciplinary field concerned with molecular effects afforded through non-covalent molecular interactions. The increased interest in the literature towards nanoscale devices, through modulation of molecular function, has seen the renaissance of supramolecular chemistry as function progresses from solution to surface. Heterosupramolecular chemistry follows the architectural principles of supramolecular chemistry and embraces both covalent and non-covalent interactions of condensed phase surfaces and molecular components. A modular approach to device architecture was applied as a novel method of performing photocatalysis under visible light illumination. The application of heterosupramolecular assembly to the design of photoelectrochemical cells capable of visible light induced charge separation allowed the study of interfacial processes by means of electrochemical observations. Preparation of a series of supramolecular components was undertaken as specific molecular species within a photochemical system. Starting from a synthesised bidentate ligand that incorporated an acidic functional group, 4,4'-bis(methyl)phosphonate-2,2'-bipyridine (dmpbpy) as its ethyl ester, was chelated to give the surface sensitisers, bis-(2,2'-bipyridine)-(4,4'-bis(methyl)phosphonato-2,2'-bipyridine)ruthenium(II) dichloride ([Ru(bpy)2(dmpbpy)]Cl2) and cis-bis-(4,4'-bis-(methyl)phosphonato-2,2'-bipyridine)(2,2'-bipyridine)ruthenium(II) dichloride ([Ru(dmpbpy)2(bpy)]Cl2). An electron relay moiety with an acidic functional group, 1-ethyl-1'-(2-phosphonoethyl)-4,4'-bipyridinium dichloride (EVP), was also prepared using a procedure developed by the candidate. The electronic properties of the prepared photosensitisers were examined by theoretical quantum chemical TD-DFT calculations on the molecular structures and singlet excitations were discussed in relation to experimental data. This identified that the lowest lying LUMO states were consistently occupied by 2,2'-bipyridine (bpy) and this was speculated to be a factor affecting quantum injection yields. The effect of microwave modification of colloidal TiO2 suspensions under extended periods of treatment was investigated. Nanoparticles of TiO2 were compared and contrast to similar convection hydrothermally treated TiO2 and a commercial titania product, namely Degussa P25, both of which are utilised in device fabrication. The investigation identified that extended periods of microwave hydrothermal treatment do not greatly enhance the crystallinity and primary grain size of TiO2. The heterosupramolecular assembly of a multi-component photochemical system was constructed from prepared molecular and condensed phase components. It was demonstrated that this device was capable of inducing a photochemical reaction in H2O under irradiation with  > 420 nm in the absence of an organic electron donor. Interpretation of the photocurrents obtained from this assembly provided understanding of photochemical reactions under low light intensities. Optimised conditions for the photochemical reaction was determined to be pH = 5 and illumination yielded = 0.0036% with an apparent quantum yield (AQY) = 1.6%. Photocatalytic decomposition of organic compounds in a dye-sensitised photoelectrocatalytic cell was investigated for the complete mineralisation of EDTA into CO2, H2 and simple amines and interpreted through photocurrent observations. This was extended to a broad range of organic compounds of various solution concentrations as a simulated industrial waste stream. Photooxidation gave unique photocurrent-time profiles which identified two distinct interfacial processes by mathematical treatment of photocurrent transients with a kinetic model. Kinetic parameters were proposed as a factor for qualitative discrimination of the organic compounds. The implications of these results for heterogeneous catalysis were discussed and the formation of Host-Guest complexes as a method of molecular sensing and as specific photocatalytic receptors was proposed.

L'hydrogène gazeux va être produit par la corrosion anaérobique des containers dans le stockage géologique de déchets radioactifs. Ce gaz peut avoir un impact sur la stabilité de la couche géologique, du fait d'une part de son caractère réducteur et d'autre part de sa production en continu pendant environ 100 000 ans. Une augmentation de pression locale peut affecter les propriétés hydro-gazo dynamiques des transferts en hydrogène. Le caractère réducteur de H2 peut modifier les propriétés d'oxydo-réduction de l'argilite du Callovo-Oxfordien (COx) et les propriétés hydrauliques de la barrière, et donc (1) sa minéralogie, (2) la spéciation des radionucléides sortant du container et (3) leur transfert. De plus, si le transport de l'hydrogène gazeux est difficile au sein de la couche géologique, l'augmentation de pression pourrait en induire la fissuration et ainsi créer des chemins préférentiels favorables à cette migration. Un dispositif expérimental a été mis en place afin d'évaluer tant la pression d'entrée de H2(g) que les paramètres de transport par perméation et diffusion à travers le COx. La pression d'entrée de l'hydrogène gazeux au sein de l'argilite du Callovo-Oxfordien saturé est comprise entre 49 et 63 bar. Sachant que la pression maximale attendue est d'environ 80 bar, on pourra donc avoir un déplacement du gaz dans la roche saturée en eau. Pour une saturation supérieure à 0,90 et avec T = 23°C, la perméabilité mesurée est proche de 10-23 m2 et le coefficient de diffusion de 10-12 m2.s-1. Ceci laisse donc envisager un déplacement lent de l'hydrogène dans la roche, par exemple il lui faudra environ 31 710 ans pour traverser un mètre de roche sous l'effet de la diffusion. Il a également été mis en évidence que les paramètres de transport dépendent essentiellement de la saturation de l'échantillon et dépendent peu de la température. Concernant la réactivité, dans des conditions proches de celles dans le stockage, H2 va réduire jusqu'à 9 wt% du Fe(III) structural sous 90°C et PH2 = 5 bar. Cette réaction n'est pas totale et le mécanisme majoritaire va être la sorption de gaz. Les niveaux d'hydrogène ainsi prélevés par le solide atteignent 0,05 wt% à 90°C et PH2 = 0,45 bar. Ce phénomène dépend fortement de la saturation de l'échantillon en eau du fait de la compétition entre H2 et H2O pour se sorber sur les sites de sorption à la surface de l'échantillon. Au total jusqu'à 18 m3 de H2 vont se sorber par m3 de COx sous PH2 = 0,45 bar et T = 90°C en conditions sèches. Ce processus va permettre, en complément du transport de gaz, de diminuer localement la pression en hydrogène. / Hydrogen gas will be produced by anaerobic corrosion of radioactive waste containers in the geological repository. This gas could affect the geological layer (Callovo-Oxfordian) stability, first due to its reductive capacity and then also due to its continuous production for about 100,000 years. The local pressure increase could affect the properties of hydro-gaseous dynamic of hydrogen transfers. The reductive capacity of H2 could change the redox properties of the Callovo-Oxfordian and the barrier hydraulic properties, and therefore (1) its mineralogy, (2) the speciation of outgoing radionuclides and (3) their transfer. Moreover, if the hydrogen gas transport is difficult within the geological layer, the pressure increase could cause cracking and create preferential pathways for radionuclides migration. An experimental device was developed to measure the entry pressure of H2(g) and transport parameters as permeability and diffusion coefficient through the COx. The entry pressure is estimated to be between 49 and 63 bar. Knowing that the maximum expected pressure is about 80 bar, there may therefore be a displacement of hydrogen gas into the water saturated clayrock. Moreover, for a saturation greater than 0.90 and at T = 23°C, permeability is measured to be close to 10-23 m2 and the diffusion coefficient to be as low as 10-12 m2.s-1. Therefore hydrogen gas will move slowly in the geological layer, for example it will take about 31,710 years to go through one meter of clayrock by diffusion. These transport parameters are found to depend mainly on the sample water saturation and not much on temperature. Regarding hydrogen reactivity, under conditions close to those in the storage, H2 will reduce up to 9 wt% of structural Fe (III) at 90°C and PH2 = 5 bar. This reaction is not complete and hydrogen gas will mainly sorb on the material, with a sorption up to 0.05 wt% at 90°C and PH2 = 0.45 bar. This process depends strongly on the water saturation of the sample, because of a competition between H2 and H2O to sorb on the surface. As a whole, more than 18 m3 of H2 per m3 of COx will sorb in dried conditions. This process will allow, during gas transport, to reduce locally the hydrogen pressure.

O objetivo deste trabalho foi enriquecer consórcio microbiano a partir de mistura de lodo granular de digestor anaeróbio de fluxo ascendente sob condições fototróficas anoxigênicas. Por meio de técnica de biologia molecular foi possível identificar 17 unidades taxonômicas operacionais (UTO) no consórcio microbiano, dentre as quais seqüências similares a Rhodobacter, gênero amplamente citado nos estudos de produção de gás hidrogênio por bactérias fototróficas. Exames microscópicos do consórcio fototrófico indicaram predomínio de bacilos Gram-negativos. Ensaios sob condições fototróficas foram realizados com dois meios de cultivo (RCVB e FANG) e os seguintes substratos orgânicos: ácido acético, butírico, cítrico, lático e málico, empregados como fonte de carbono, tanto para o crescimento celular, como para a produção do gás hidrogênio. A relação C/N inicial foi 30/4 e posteriormente 15/2, com o objetivo de favorecer o crescimento celular e a produção do \'H IND.2\'. A concentração dos substratos foi determinada de forma com que essa relação se mantivesse a mesma. O crescimento celular e consumo dos ácidos orgânicos foram similares para os dois meios de cultivo empregados. Entretanto, a produção do gás hidrogênio foi maior nos ensaios com o meio FANG. Dentre os substratos utilizados o consumo dos ácidos cítrico e málico foram os maiores (~100%), para concentrações iniciais de 3,3 g/L e 2,6 g/L, respectivamente. O menor consumo 25% foi observado em meio RCVB e ácido acético (2,5 g/L). O crescimento da biomassa variou de 0,06 g/L a 1,1 g/L, enquanto que a velocidade máxima específica de crescimento variou de 0,4 a 0,2 g SSV/L.d entre os substratos utilizados. A menor e maior concentração de hidrogênio foram de 8,5 e 22 mmol \'H IND.2\'/L, para os reatores alimentados com ácido lático e málico em meio FANG, respectivamente. Pôde-se concluir que o consórcio fototrófico enriquecido foi capaz de utilizar os ácidos orgânicos para produção do gás hidrogênio. / The aim of this work was enrich a mixture of granular sludge of an up flow anaerobic sludge blanket (UASB) under anoxygenic phototrophic conditions. The techniques of molecular biology identified 17 operational taxonomic units (UTO) in the microbial consortium among the sequences analised, which were similar to Rhodobacter, genus widely cited in studies of hydrogen gas production by phototrophic bacteria. Microscopic examinations of the phototrophic consortium showed predominance of Gram-negative bacilli. Tests were conducted under phototrophic conditions with two culture media (RCVB and FANG) and the following organic substrates: acetic, butyric, citric, lactic and malic acids that were used as carbon source for both cell growth and for the hydrogen gas production. The carbon nitrogen ratio (C/N) in the preliminaries tests was 30/4 and then it was changed to15/2 in order to improve the cell growth and hydrogen production. The concentration of substrates was determined for remain the same carbon/nitrogen ratio among the substrates. The cell growth and consumption of organic acids were similar for the two culture media used. However, the production of hydrogen gas was higher in trials with the medium FANG. Among the substrates used, the consumption of malic and citric acids were the highest (~100%) for initial concentrations of 3.3 g/L and 2.6 g/L, respectively. The shortest consumption (25%) was observed for the cells that grew on acetic acid, 2.5 g/L in RCVB culture medium. The growth of the biomass varied from 0.06 g/L to 1.1 g/L, whereas the maximum specific growth rate ranged from 0.4 to 0.2 g VSS/L.d between the substrates used. The lowest and highest concentrations of hydrogen were 8.5 and 22 mmol \'H IND.2\'/L for the reactor fed with lactic acid and malic acid in FANG\'s medium, respectively. It was concluded that the phototrophic consortium was able to use those organic acids for the production of hydrogen gas.

Today’s society is standing in front of a revolution where fossil energy should be replaced with renewable energy. Governmental agencies and policy makers have formed goals and regulations to become greener, and the organisation Fossil Free Sweden has published roadmaps for fossil free competitiveness. Therefore, this report has connected Paroc’s operations with a roadmap for fossil free competitiveness to form a strategic environmental plan. Early, it was recognized that the field was big and a limitation to CO2-emissions during production were established. The facts were gathered mostly throughout literature studies, scientific publications/articles, and personal communication with personnel at Paroc/Owens Corning. The results gave a description over fossil free competitiveness for the construction sector, previous, and current sustainability efforts at Paroc. After that, the report lifted suggestions of modifications to the mainstream process. Focus laid on the reduction of coke, propane, and dolomite. Later, the report discussed a possible strategy to become fossil free by 2045. It found out that there are many approaches to become climate neutral. Moreover, a need for practical testing of the solutions in the mainstream processes, and that emissions can be calculated in an absolute of relative way.