Abstract The energy consumption around the globe is on the rise due to the exponential population growth and urbanization. There is a need for alternative and non-conventional energy sources, which are CO2-neutral, and a need to produce less or no environmental pollutants and to have high energy efficiency. One of the alternative approaches is hydrogen economy with the fuel cell (FC) technology which is forecasted to lead to a sustainable society. Hydrogen (H2) is recognized as a potential fuel and clean energy carrier being at the same time a carbon-free element. Moreover, H2 is utilized in many processes in chemical, food, metallurgical, and pharmaceutical industry and it is also a valuable chemical in many reactions (e.g. refineries). Non-renewable resources have been the major feedstock for H2 production for many years. At present, ~50% of H2 is produced via catalytic steam reforming of natural gas followed by various down-stream purification steps to produce ~99.99% H2, the process being highly energy intensive. Henceforth, bio-fuels like biomass derived alcohols (e.g. bio-ethanol and bio-glycerol), can be viable raw materials for the H2 production. In a membrane based reactor, the reaction and selective separation of H2 occur simultaneously in one unit, thus improving the overall reactor efficiency. The main motivation of this work is to produce H2 more efficiently and in an environmentally friendly way from bio-alcohols with a high H2 selectivity, purity and yield. In this thesis, the work was divided into two research areas, the first being the catalytic studies using metal decorated carbon nanotube (CNT) based catalysts in steam reforming of ethanol (SRE) at low temperatures (<450 °C). The second part was the study of steam reforming (SR) and the water-gas-shift (WGS) reactions in a membrane reactor (MR) using dense and composite Pd-based membranes to produce high purity H2. CNTs were found to be promising support materials for the low temperature reforming compared to conventional catalyst supports, e.g. Al2O3. The metal/metal oxide decorated CNTs presented active particles with narrow size distribution and small size (~2–5 nm). The ZnO promoted Ni/CNT based catalysts showed the highest H2 selectivity of ~76% with very low CO selectivity <1%. Ethanol was shown to be a more suitable and viable source for H2 than glycerol. The dense Pd-Ag membrane had higher selectivity but a lower permeating flux than the composite membrane. The MR performance is also dependent on the active catalyst materials and thus, both the catalyst and membrane play an important role. Overall, the membrane–assisted reformer outperforms the conventional reformer and it is a potential technology in pure H2 production. The high purity of H2 gas with a CO-free reformate for fuel cell applications can be gained using the MR system. / Tiivistelmä Maailman energiankulutus on kasvussa räjähdysmäisen väestönkasvun ja voimakkaan kaupungistumisen myötä. Tällä hetkellä energian tuottamisen aiheuttamat ympäristöongelmat ja taloudellinen epävarmuus ovat seikkoja, joiden ratkaisemiseksi tarvitaan vaihtoehtoisia ja ei-perinteisiä energialähteitä, joilla on korkea energiasisältö ja jotka tuottavat vähän hiilidioksidipäästöjä. Eräs vaihtoehtoisista lähestymistavoista on vetytalous yhdistettynä polttokennotekniikkaan, minkä on esitetty helpottavan siirtymistä kestävään yhteiskuntaan. Vety on puhdas ja hiilivapaa polttoaine ja energian kantaja. Lisäksi vetyä käytetään monissa prosesseissa kemian-, elintarvike-, metalli- ja lääketeollisuudessa ja se on arvokas kemikaali monissa prosesseissa (mm. öljynjalostamoissa). Uusiutumattomat luonnonvarat ovat olleet tähän saakka merkittävin vedyn tuotannon raaka-aine. Tällä hetkellä noin 50 % vedystä tuotetaan maakaasun katalyyttisellä höyryreformoinilla. Puhtaan (yli 99,99 %) vedyn tuotanto vaatii kuitenkin useita puhdistusvaiheita, jotka ovat erittäin energiaintensiivisiä. Integroimalla reaktio- ja puhdistusvaihe samaan yksikköön (membraanireaktori) saavutetaan huomattavia kustannussäästöjä. Biopolttoaineet, kuten biomassapohjaiset alkoholit (bioetanoli ja bioglyseroli), ovat vaihtoehtoisia lähtöaineita vedyn valmistuksessa. Tämän työn tavoitteena on tuottaa vetyä bioalkoholeista tehokkaasti (korkea selektiivisyys ja saanto) ja ympäristöystävällisesti. Tutkimus on jaettu kahteen osaan, joista ensimmäisessä tutkittiin etanolin katalyyttistä höyryreformointia matalissa lämpötiloissa (<450 °C) hyödyntämällä metallipinnoitettuja hiilinanoputkia. Työn toisessa osassa höyryreformointia ja vesikaasun siirtoreaktioa tutkittiin membraanireaktorissa käyttämällä vedyn tuotantoon tiheitä palladiumpohjaisia kalvoja sekä huokoisia palladiumkomposiittikalvoja. Hiilinanoputket (CNT) havaittiin lupaaviksi katalyyttien tukimateriaaleiksi verrattuna tavanomaisesti valmistettuihin tukiaineisiin, kuten Al2O3. CNT-tukiaineelle pinnoitetuilla aktiivisilla aineilla (metalli-/metallioksidit) todettiin olevan pieni partikkelikoko (~2–5 nm) ja kapea partikkelikokojakauma. Sinkkioksidin (ZnO) lisäyksellä Ni/CNT-katalyytteihin saavutettiin korkea vetyselektiivisyys (~76 %) ja erittäin alhainen hiilimoksidiselektiivisyys (<1 %). Etanolin todettiin olevan parempi vedyn raaka-aine kuin glyserolin. Tiheillä Pd-Ag-kalvoilla havaittiin olevan vedyn suhteen korkeampi selektiivisyys mutta matalampi vuo verrattuna palladiumkomposiittikalvoihin. Membraanireaktorin suorituskyky oli riippuvainen myös katalyytin aktiivisuudesta, joten sekä kalvolla että katalyyttimateriaalilla oli merkittävä rooli kyseisessä reaktorirakenteessa. Yhteenvetona voidaan todeta, että membraanierotukseen perustuva reformointiyksikkö on huomattavasti perinteistä reformeriyksikköä suorituskykyisempi mahdollistaen tehokkaan teknologian puhtaan vedyn tuottamiseksi. Membraanitekniikalla tuotettua puhdasta vetyä voidaan hyödyntää mm. polttokennojen polttoaineena.

Abstract The objective of this thesis is to demonstrate multi-dimensional carbon nanotube (CNT) structures in combination with various active materials in order to evaluate their performance in electrode applications such as cold emitters, electric double-layer capacitors (EDLC), and electrochemical sensor/catalyst devices. As the host materials for other active materials, the construction of multi-dimensional CNT nanostructures in this thesis is achieved by two different approaches. In the first, direct growth of 3-dimensional carbon nanostructures by catalytic chemical deposition to produce filamentary carbon as well as vertically aligned forests was applied. The second route that was utilized encompassed the immobilization of CNTs from dispersions to form 2-dimensional surface coatings as well as self-supporting porous buckypapers. Carbonaceous nanocomposites of the active materials are obtained by a number of different methods such as (i) growing nanotubes and filamentous structures on porous Ni catalyst structures, (ii) impregnating CNTs with organic receptor molecules or with Pd nanoparticles, (iii) plating and replacing Cu with Pd on the nanotubes by chemical and galvanic reactions, (iv) annealing W evaporated on CNTs to form CNT-WC composites in solid-solid reactions and (v) reacting S vapor with W coated on CNTs to synthesize CNT-WS2 edge-on lamellar structures of the dichalcogenide in the vertically aligned CNT forests. The 3-dimensional carbon-Raney®Ni composite electrodes show reasonable specific capacitance of ~12 F·g-1 in electric double-layer capacitors as well as a low turn-on field (<1.0 V·µm-1) in field emitter devices. CNT-Nafion®-trifluoroacetylazobenzene coatings on glassy carbon electrodes outperform their Nafion®-trifluoroacetylazobenzene counterparts in electrochemical sensing of different amine compounds (e.g. 10 mM cadaverine, putrescine or ammonia). Cu and CuPd/buckypaper composites display catalytic activity in electrocatalytic oxidation of methanol in alkaline media. On the other hand, nanocomposites of WC and WS2 with aligned CNT forest exhibit a promising performance in hydrogen evolution reactions with an overpotential between -0.5 and -0.7 V at pH~1. In addition, these respective CNT forest aligned nanocomposites also demonstrate a novel method to obtain macroscopic 3-dimensional catalytic electrode assemblies. The results in this thesis elucidate the combination of carbon based nanostructures with organic and inorganic materials as a feasible and versatile approach to produce electrodes for several applications. The following studies of each active carbonaceous composite are expected to boost the technological innovation in relevant fields and initiate further development for commercial exploitation. / Tiivistelmä Työn tavoitteena oli demonstroida moniulotteisia hiilinanoputkirakenteita (CNT), joihin yhdistetään erilaisia aktiivisia materiaaleja sekä arvioida niiden suorituskykyä elektrodisovelluksissa, kuten kenttäemitterissä, sähköisissä kaksoiskerroskondensaattoreissa ja sähkökemiallisissa anturi- ja katalyyttikomponenteissa. Moniulotteisten CNT-nanorakenteiden konstruoiminen muiden aktiivisten materiaalien isäntämateriaaliksi toteutettiin kahdella tavalla. Ensimmäisessä toteutuksessa sovellettiin katalyyttis-kemiallista pinnoitusta, jolla kasvatettiin suoraan kolmiulotteisia hiilinanorakenteita sekä kuitumaisena hiilenä että pystysuuntaan orientoituneina hiilinanoputkimetsinä. Toinen päämenetelmä oli hiilinanoputkien immobilisointi dispersioista kaksiulotteisiksi pinnoitteiksi ja itsetukeutuviksi huokoisiksi hiilinanoputkipapereiksi. Hiiltä sisältäviä aktiivisten materiaalien nanokomposiitteja valmistettiin useilla menetelmillä, kuten (i) kasvattamalla nanoputkia ja kuitumaisia rakenteita huokoisiin Ni-katalyyttirakenteisiin, (ii) kyllästämällä hiilinanoputkia orgaanisilla reseptorimolekyyleillä tai Pd-nanopartikkeleilla, (iii) pinnoittamalla ja korvaamalla nanoputkien päällä olevaa kuparia palladiumilla kemiallisten ja galvaanisten reaktioiden avulla, (iv) hehkuttamalla hiilinanoputkien pinnalle höyrystettyä wolframia (W) muodostamaan CNT-WC-komposiitteja kiinteä–kiinteä-reaktiolla sekä (v) antamalla rikkihöyryn reagoida W-pinnoitettujen hiilinanoputkien kanssa lamellaaristen CNT-WS2-kalkogenidirakenteiden syntetisoimiseksi pystysuuntaan orientoituneisiin CNT-metsiin. Kolmiulotteisilla hiili–Raney®Ni-komposiittielektrodeilla saavutetaan kohtuullinen ominaiskapasitanssi (~12 F·g-1) sähköisissä kaksoiskerroskondensaattoreissa ja pieni kytkeytymiskenttä (<1,0 V·μm-1) kenttäemitterikomponenteissa. CNT-Nafion®-trifluoroasetyyliatsobentseeni-pinnoitteet lasimaisilla hiilielektrodeilla ovat selvästi parempia erilaisten amiiniyhdisteiden (esimerkiksi 10 mM kadaveriini, putreskiini tai ammoniakki) sähkökemiallisessa havaitsemisessa kuin vastaavat Nafion®-trifluoroasetyyliatsobentseeni-pinnoitteet. Cu- ja CuPd-hiilinanoputkipaperikomposiitit osoittavat katalyyttistä aktiivisuutta metanolin sähkökatalyyttisessä hapettumisessa emäksisessä väliaineessa. Toisaalta WC- ja WS2-yhdisteiden ja orientoituneiden CNT-metsien muodostamat nanokomposiitit osoittavat lupaavaa suorituskykyä vedynmuodostamisreaktiossa -0,5…-0,7 V ylipotentiaalilla, ja nämä myös demonstroivat uutta menetelmää makroskooppisten kolmiulotteisten katalyyttisten elektrodirakenteiden toteuttamiseksi. Väitöskirjan tulokset osoittavat, että hiilipohjaisten nanorakenteiden ja orgaanisten/epäorgaanisten materiaalien yhdistäminen on toteuttamiskelpoinen ja monipuolinen lähestymistapa elektrodien valmistamiseksi useisiin sovelluksiin. Kunkin työssä esitetyn aktiivista hiiltä sisältävän komposiitin tutkimuksen odotetaan lisäävän kyseisen alan teknisiä innovaatioita ja synnyttävän lisää kehitystyötä tutkimuksen kaupalliseksi soveltamiseksi.

L'épuisement annoncé dans les prochaines décennies des ressources fossiles qui fournissent actuellement plus de 70% du carburant consommé dans les transports terrestres, aériens et maritimes au niveau mondial, incite à l'identification et le développement de nouvelles sources d'énergies renouvelables. La production de biocarburants issue de l'exploitation de la biomasse représente une des voies de recherche les plus prometteuses. Si la première génération des biocarburants (production à partir de plantes sucrières, de céréales ou d'oléagineux) atteint ses limites (concurrence avec les usages alimentaires, en particulier), la deuxième génération, produite à partir de ressources carbonées non alimentaires (lignocellulosique, mélasse, vinasse...), pourrait prendre le relais, une fois que les procédés de conversion seront suffisamment maîtrisés. À plus long terme, une troisième génération pourrait voir le jour, qui reposerait sur l'exploitation de la biomasse marine (microalgues, en particulier) mais où de nombreux verrous restent toutefois à lever : optimisation des procédés de culture et de récolte, extraction à coût réduit, optimisation des voies métaboliques etc. Il est à retenir que la stratégie nationale de recherche et d'innovation (SNRI) a retenu quatre « domaines clés » pour l'énergie : le nucléaire, le solaire photovoltaïque, les biocarburants de deuxième génération et les énergies marines. Ceux-ci sont complétés, au nom de leur contribution potentielle à la lutte contre le changement climatique, par le stockage du CO2, la conversion de l'énergie (dont les piles à combustible) et l'hydrogène. Le présent projet de recherche s'intéresse à explorer des voies d'amélioration de l'efficacité de la biotransformation de matière organique non alimentaire de nature industrielle en biocarburants de deuxième génération. En particulier, on s'intéressera à deux aspects complémentaires : l'optimisation des organismes microbiens et des voies métaboliques pour l'amélioration du rendement biologique de fabrication de biocarburants ; l'optimisation des procédés de mise en culture des microorganismes et d'extraction des biocarburant. Le projet de thèse consiste à mettre en œuvre les biotechnologies blanches, la biologie de synthèse et le génie des procédés pour la caractérisation de souches bactériennes, de leurs voies métaboliques et de prototypes expérimentaux pour la fabrication de biocarburants, de méthane et d'hydrogène à partir de rejets provenant de l'industrie sucrière de La Réunion, à savoir la mélasse ou la vinasse. Ce projet permettrait d'envisager de nouvelles perspectives de valorisation pour ces déchets industriels et de participer à la construction, à terme, d'une industrie réunionnaise durable des biocarburants et de l'hydrogène. / Hydrogen is a candidate for the next generation fuel with a high energy density and an environment friendly behavior in the energy production phase. Micro-organism based biological production of hydrogen currently suffers low hydrogen production yields because the living cells must sustain different cellular activities other than the hydrogen production to survive. To circumvent this, a team have designed a synthetic cell-free system by combining 13 different enzymes to synthesize hydrogen from cellobiose. This assembly has better yield than microorganism-based systems. We used methods based on differential equations calculations to investigate how the initial conditions and the kinetic parameters of the enzymes influenced the productivity of a such system and, through simulations, to identify those conditions that would optimize hydrogen production starting with cellobiose as substrate. Further, if the kinetic parameters of the component enzymes of such a system are not known, we showed how, using artificial neural network, it is possible to identify alternative models that allow to have an idea of the kinetics of hydrogen production. During our study on the system using cellobiose, other cell-free assemblies were engineered to produce hydrogen from different raw materials. Interested in the reconstruction of synthetic systems, we decided to conceive various tools to help the automation of the assembly and the modelling of these new synthetic networks. This work demonstrates how modeling can help in designing and characterizing cell-free systems in synthetic biology.

This master thesis deals with the topic of alternative production of hydrogen as the energy carrier of the future. The primary focus is on the production of hydrogen based on photocatalytical water splitting in the presence of semiconductor materials (especially modified and unmodified TiO2). The aim of the thesis is a synthesis of nanostructured oxide, graphene/graphene oxide particles and its composites, and a study of its structures and photocatalytical properties regarding photolysis of water. Products of the syntheses are described from the point of view of phase composition, surface area and photocatalytical activity. The main output of the thesis is a discussion of the influence of alkaline complex forming reagents on the hydrothermal low-temperature synthesis of biphasic TiO2, and a study of the influence of graphene/graphene oxide modification on photocatalytical activity of biphasic TiO2.

The diplom work is focused on the design of transit bus. I pointed out two aim: design from the view of future the perspektive; environmental drive and create timeless bus design, which should be correspond with the drive of near future. It was chosen the most ecological drive with help of hydrogen and fuel cells. This drive was developed in detail. Like reserve and helpful energy source was used ultrakapacitors and fotovoltaic cells. Bus design tries to realize the future requirement of carriers and regarding to its oscillating along big cities so represent with its design the used drived unit. The internal ordering of interior tries to realize the together and future reguirements on the sit ergonomics, store of bagages, hygienic requirements and good lookout of passengers. The name and logo of transit bus arrise from reference to fuell, environment and fuell cell.

Les travaux de cette thèse sont centrés sur le développement de systèmes moléculaires en solution homogène pour la production photocatalytique de dihydrogène dans l'eau utilisant des catalyseurs de cobalt à ligands pentadentate tétrapyridinique ou tétra- et pentaaza macrocycliques. Associés au photosensibilisateur et à l’ascorbate comme donneur d’électron sacrificiel, les complexes à ligands macrocycliques présentent d’excellentes performances pour la production d’H2, bien supérieures à celles des complexes à ligands polypyridiniques en termes d’efficacité et de stabilité, en raison de la grande stabilité de leur état réduit «Co(I)». Enfin, [Ru(bpy)3]2+ a pu être substitué par un colorant organique très robuste du type triazatriangulénium conduisant à un système photocatalytique encore plus performant. Ces résultats démontrent que les colorants organiques sont une alternative viable aux photosensibilisateurs à base de métaux nobles, même en milieu aqueux acide. / The work of this manuscript is focused on the design of molecular systems in homogeneous solution for photocatalytic production of molecular hydrogen in water using cobalt catalysts with pentadentate tetrapyridinic and tetra- and pentaza macrocyclic ligands. In association with [Ru(bpy)3]2+ as photosensitizer and sodium ascorbate as sacrificial electron donor, the macrocycle based catalysts display high performances for H2 production, far exceeding those of the polypyridine based catalysts, both in terms of activity and stability, because of the stability of their reduced state «Co(I)». Finally, [Ru(bpy)3]2+ was successfully substituted with a robust organic dye belonging to the triazatriangulenium family, leading to an even more efficient photocatalytic system. These results demonstrate well that organic dyes are a truly efficient alternative to noble metal based photosensitizers, even in acidic aqueous medium.

Hydrogen has the potential to become an important energy carrier in the future with many areas of applications, as a clean fuel for transportation, heating, power generation in places where electricity use is not fit, etc. Already today hydrogen plays a key role in numerous industries such as petroleum refineries and chemical industries. There are different production methods for hydrogen. Today, natural gas reforming is the most commonly used. With the growing importance of green production paths, hydrogen production by electrolysis is expected to grow. Two main electrolyzer technologies are used today; alkaline and polymer electrolyte membrane electrolyzer. High-temperature electrolyzers are also interesting techniques, where solid oxide is under development and molten carbonate electrolyzers is researched. In this thesis, a comparative life cycle analysis was performed on the alkaline and molten carbonate electrolyzer. Due to inaccurate inventory data for the molten carbonate electrolyzer, those results are excluded from the published thesis. The environmental performance of the alkaline electrolyzer technology was compared to that of the solid oxide and the polymer electrolyte membrane electrolyzers. The system boundaries were set as cradle to gate. Thereby, the life cycle steps included in the study are raw material extraction, electrolyzer manufacturing, hydrogen production, and transports in between these steps. The functional unit was chosen as 100 kg produced hydrogen gas. The results show that the polymer electrolyte membrane electrolyzer has the lowest environmental impact out of the compared technologies. It is also determined that the lifetime and the current density of the electrolyzers have significant impact on their environmental performance. Moreover, it is established that electricity for hydrogen production has the highest environmental impact out of the electrolyzers life cycle steps. Therefore, it is important to make sure that the electricity used for hydrogen production derives from renewable sources. / Vätgas har potential att spela en viktig roll som energibärare i framtiden med många användningsområden, såsom ett rent bränsle för transporter, uppvärmning, kraftförsörjning där elproduktion inte är lämpligt, med mera. Redan idag är vätgas ett viktigt inslag i flera industrier, där ibland raffinaderier och kemiska industrier. Det finns flera metoder för att producera vätgas, där reformering av naturgas är den största produktionsmetoden idag. I framtiden spås vätgasproduktion med elektrolys bli allt viktigare, då hållbara produktionsprocesser prioriteras allt mer. Idag används främst två elektrolysörtekniker, alkalisk och polymerelektrolyt. Utöver dessa är högtemperaturelektrolysörer också intressanta tekniker, där fastoxidelektrolysören är under utveckling och smältkarbonatelektrolysören är på forskningsstadium. I det här examensarbetet har en jämförande livscykelanalys utförts på alkalisk- och smältkarbonatelektrolysören. På grund av felaktiga indata för smältkarbonatelektrolysören har dessa resultat uteslutits från den publika rapporten. Miljöpåverkan från den alkaliska elektrolysören har sedan jämförts med miljöpåverkan från fastoxid- och polymerelektrolytelektrolysörerna. Systemgränserna sattes till vagga till grind. De livscykelsteg som inkluderats i studien är därmed råmaterialutvinning, elektrolysörtillverkning, vätgasproduktion och transporter mellan dessa steg. Den funktionella enheten valdes till 100 kg producerad vätgas.  Resultaten visar att polymerelektrolytteknologin har den lägsta miljöpåverkan utav de tekniker som jämförts. Resultaten påvisar också att livstiden och strömtätheten för de olika teknikerna har signifikant påverkan på teknikernas miljöpåverkan. Dessutom fastslås att elektriciteten för vätgasproduktion har högst miljöpåverkan utav de studerade livscykelstegen. Därför är det viktigt att elektriciteten som används för vätgasproduktionen kommer ifrån förnybara källor.

In conjunction with Sweden's goal of reducing emissions and dependence on fossil fuels in the transport sector, hydrogen technology has received considerable attention. Today, several studies are being carried out into hydrogen technology that focus on developing the production, application, storage and distribution of hydrogen. Energimyndigheten is investigating various strategies for hydrogen development to increase hydrogen production, develop green transports and opportunities for energy storage in Sweden. This study is about estimating the potential for hydrogen in heavy-duty vehicles in Västerås and investigating various possibilities for local hydrogen production. Gasification plants with capacities of 1, 5 and 10 MW are studied to analyze the gasification plant's design, operating conditions, costs and investment profitability. In addition, it is investigating the possibility of building a hydrogen filling station with hydrogen produced by an electrolysis plant in Rocklunda. For the electrolysis plant in Rocklunda, alkaline electrolysis from Nel Hydrogen (A150 and A300) with a power of 660 and 1320 kW and a daily production of 320 and 640 kg of hydrogen respectively are investigated. The electrolysis is connected to the electricity grid and the PV system in Rocklunda, while waste heat from the electrolysis is used to balance the district heating network.   The results of this study show that the potential for hydrogen can vary depending on the number of heavy hydrogen-powered vehicles, the mileage and the depreciation period. Different scenarios are discussed to get an estimation of what the development of hydrogen demand may look like. For a long-term scenario with high hydrogen demand, hydrogen production with a gasification plant is considered suitable. The total investment costs are estimated at 2.3, 4.7 and 7.7 million euros for 1, 5 and 10 MW plants. The production cost for each plant is estimated at 3.45, 2.28 and 2.12 euros per kg of hydrogen. The results also show that efficiency and costs for operation and maintenance are factors that have the greatest impact on production costs. For the net present value, efficiency and sales price are two factors that constitute the greatest impact.  For the A150 and a hydrogen filling station with a storage capacity of 400 kg per day, the total investment cost is estimated at 2.5 million euros. For the A300 and a hydrogen filling station with a capacity of 800 kg per day, the total investment cost amounts to 4.7 million euros. MATLAB is used to optimize hydrogen production that meets the estimated hydrogen demand and minimize costs in Rocklunda. The production cost per kg of hydrogen is estimated at 8 and 7 euros for the A150 and A300. For the electrolysis plant, the results show that the price of electricity has the greatest impact on the production cost, while the net present value is most affected by the electricity price and sales price for hydrogen. Furthermore, the results show that approximately 70% of the annual hydrogen production takes place with the electricity grid between 21 and 05 when the electricity price is low, which means that the hydrogen is not classified as green hydrogen.   The conclusion that has been drawn in this study is that hydrogen enables the electrification of heavy-duty vehicles with long driving distances. In 2024, it is expected that there will be the possibility of selling produced green hydrogen to build hydrogen filling stations in Sweden. Hydrogen production with an electrolysis plant in Rocklunda is a suitable method that can meet the hydrogen demand in the short term. However, this means higher costs for one kg of produced hydrogen.   To produce green hydrogen, green electricity from local electricity grid must be used in the electrolysis. Increased capacity on the PV system in Rocklunda is an alternative for increasing the proportion of green hydrogen. Hydrogen production with a gasification plant entails high investment costs but is suitable for large-scale production, which means that a high demand in the market is required to ensure investment profitability.

In face of climate change, Europe and other global actors are in the process of transitioning to carbon-neutral economies, aiming to phase out of fossil fuels and power industries with renewable energies. Hydrogen is going to play a crucial role in the transition, replacing fossil fuels in hard-to-decarbonize industries and acting as energy carrier and energy storage for renewable electricity. However, the hydrogen production method with the lowest carbon intensity, water electrolysis in combination with renewable electricity, is often not cost competitive to other production methods. Even though policies and initiatives are providing subsidies to scale up low-carbon hydrogen production, companies hesitate to invest due to the complexity of hydrogen production systems and the uncertainties of cost competitiveness. This research aims to develop a tool for optimizing the capacity of a water electrolysis system to produce low-carbon hydrogen and to lay the groundwork for optimizing the operation of electrolysis hydrogen production plants. The objective is to find the optimal plant capacity to achieve the lowest cost of hydrogen production for a defined hydrogen demand and energy supply. The scope is limited to the electrolysis system as optimizing asset which is modeled with technology-specific costs and characteristics, gained from manufacturer interviews and internal company data. This includes the often neglected characteristics of load-dependent efficiency and degradation effects. Further, the tool is enabled to buy and sell electricity on the spot market according to predicted prices in order to minimize the electricity costs. The developed tool is tested, benchmarked and applied to two different industry-based test scenarios in Germany and Portugal. The test scenario in Germany describes a mid-scale hydrogen production case for a transport application with a demand increase over 10 years (80 to 1,800 tons per year) and regional renewable energy supply via power purchase agreements. The lowest costs of hydrogen production for this scenario can be reached with an alkaline electrolysis system of a capacity of 16 MWel considering only renewable energy sources, achieving a LCOH of 4.75 €/kg of green hydrogen. The second test scenario describes a large-scale production case in Portugal for application in the refinery industry. The yearly hydrogen demand increases from 5,000 tons up to 17,100 tons within three years and is assumed to stay constant for the residual years. The electricity for the electrolysis process is secured through large solar PV and offshore wind power purchase agreements. Utilizing the alkaline electrolysis technology with a capacity of 128 MWel, a LCOH of 3.31 €/kg of green hydrogen can be achieved at the output point of the plant. The study concludes that the optimal solution and the achievable hydrogen production costs are highly dependent on the hydrogen demand (quantity and profile), the energy supply (quantity, profile, costs), and the chosen technology (efficiency, degradation, costs) and need to be evaluated under the case-specific prerequisites. The thesis further highlights the significant impact of the electrolysis system efficiency and capital expenditures on the capacity decision and achievable hydrogen production costs. / Mot bakgrund av klimatförändringarna håller Europa och andra globala aktörer på att ställa om till koldioxidneutrala ekonomier, med målet att fasa ut fossila bränslen och driva industrier med förnybara energikällor. Vätgas kommer att spela en avgörande roll i omställningen genom att ersätta fossila bränslen i industrier som är svåra att koldioxidneutralisera och fungera som energibärare och energilagring för förnybar el. Den metod för vätgasproduktion som har lägst koldioxidintensitet, vattenelektrolys i kombination med förnybar el, är dock ofta inte kostnadsmässigt konkurrenskraftig i förhållande till andra produktionsmetoder. Även om politik och initiativ tillhandahåller subventioner för att skala upp koldioxidsnål vätgasproduktion, tvekar företagen på grund av komplexiteten i vätgasproduktionssystemen och osäkerheten kring konkurrenskraften. Denna forskning syftar till att utveckla ett verktyg för att optimera kapaciteten hos ett vattenelektrolyssystem för att producera grön vätgas och att lägga grunden för att optimera driften av elektrolysanläggningar för vätgasproduktion. Målet är att hitta den optimala anläggningskapaciteten för att uppnå den lägsta kostnaden för vätgasproduktion för en definierad vätgasefterfrågan och definierad energiförsörjning. Omfattningen är begränsad till elektrolyssystemet som en optimerande tillgång som modelleras med teknikspecifika kostnader och egenskaper, hämtade från tillverkar-intervjuer och från företags interna marknadsdata. Detta inkluderar de ofta försummade egenskaperna hos lastberoende effektivitet och degraderingseffekter. Vidare kan verktyget köpa och sälja el på spotmarknaden enligt förutspådda priser för att minimera elkostnaderna. Det utvecklade verktyget testas, jämförs och tillämpas på två olika industribaserade testscenarier i Tyskland och Portugal. Testscenariot i Tyskland beskriver en medelstor vätgasproduktion för en transporttillämpning där efterfrågan ökar över 10 år (80 till 1 800 ton per år) och regional förnybar energiförsörjning via energiköpsavtal (power purchase agreements). De lägsta kostnaderna för vätgasproduktion för detta scenario kan uppnås med ett alkaliskt elektrolyssystem med en kapacitet på 16 MWel som endast använder förnyelsebara energikällor och uppnår en LCOH på 4,75 €/kg grön vätgas. Det andra testscenariot beskriver en storskalig vätgasproduktion i Portugal för tillämpning inom raffinaderi-industrin. Det årliga vätgasbehovet ökas från 5 000 ton till 17 100 ton inom tre år och antogs förbli konstant under de återstående åren. El för elektrolysprocessen säkras genom stora energiköpsavtal (power purchase agreements) för solceller och havsbaserad vindkraft. Genom att använda alkalisk elektrolysteknik med en kapacitet på 128 MWel kan en LCOH på 3,31 €/kg grön vätgas uppnås vid anläggningens utgångspunkt. Studien visar att den optimala lösningen och de uppnåbara vätgasproduktionskostnaderna är starkt beroende av vätgasbehovet (mängd och profil), energiförsörjningen (mängd, profil, kostnader) och den valda tekniken (effektivitet, nedbrytning, kostnader) och måste utvärderas utifrån de fallspecifika förutsättningarna. Avhandlingen belyser vidare den betydande inverkan som elektrolyssystemets effektivitet och kapitalutgifter har på kapacitetsbeslutet och de uppnåeliga kostnaderna för vätgasproduktion.

In order to keep the Paris Agreement's goal of limiting global warming to well below 2°C, greenhouse gas emissions should be reduced. However, larger measures need to be implemented as it has been established that today's measures will not be enough. The Port of Gävle has plans to install a water electrolyser for hydrogen production of either Proton Exchange Membrane (PEM) or Alkaline Water Electrolysis(AWE). The size of the electrolyser will be approximately 10 MW and will have the capacity to produce 2,000 tons of fossil-free hydrogen per year that might supply 100 heavy trucks. However, it is currently cheaper with fossil hydrogen production. Therefore, an article review is conducted containing a calculation part where the purpose is to investigate the amount of by-products produced and whether they can be sold in other areas of use to make renewable hydrogen more economically competitive. Information for the study has been retrieved from databases, search engines, companies, authorities and individuals deemed relevant to the study. The by-products from the 10 MW electrolyser in the Port of Gävle have been compared with 1,5 MW and 17 MW electrolysers, then a sensitivity analysis has also beenperformed on the 10 MW electrolysers. The potentially generated heat depends on the type of electrolyser where AWE generates 77 MWh of residual heat per day and PEM potentially generates 67 MWh of residual heat per day. Furthermore, AWE needs 64 kWh of electricity to produce 1 kg of hydrogen while PEM needs 66,5 kWh of electricity per kg of hydrogen produced. Revenues from residual heat sales for AWE were estimated annually to approximately 7 million SEK and for PEM approximately 6 million SEK. For electrolysis-produced oxygen to compete with cryogenic oxygen, the price should not exceed 108 SEK/tonne. For the 10 MW electrolyser, oxygen sales are estimated to generate approximately 1,1 million SEK annually for both AWE and PEM. Total income for AWE will annually be just over 8,1 million SEK and 7.1million SEK annually for PEM. The AWE process is then preferable as it is more economically sustainable as the income from the by-products is 12% higher than PEM due to higher production of oxygen and greater generation of residual heat. / För att hålla Parisavtalets mål att begränsa den globala uppvärmningen till väl under 2°C bör utsläppen av växthusgaser minska. Däremot behöver större åtgärder genomföras då det har konstaterats att dagens åtgärder inte kommer att räcka. Gävle hamn har planer på att installera en vattenelektrolysör för vätgasproduktion av antingen Protonutbytesmembran (PEM) eller Alkalisk vattenelektrolys (AWE). Storleken på elektrolysören kommer vara ungefär 10 MW och har kapaciteten att producera 2000 ton fossilfri vätgas per år som kan försörja 100 tunga lastbilar. Dock är det i dagsläget billigare med fossil vätgasproduktion. Därför genomförs en litteraturstudie innehållande en beräkningsdel. Där syftet är att undersöka mängden biprodukter som produceras samt om de kan säljas inom andra områden för att göra förnyelsebar vätgas mer ekonomiskt konkurrenskraftig. Information för studien har hämtats från databaser, sökmotorer, företag, myndigheter och enskilda personer som ansetts relevanta för studien. Biprodukterna från 10 MW elektrolysören i Gävle hamn har jämförts med 1,5 MW och 17 MW elektrolysörer, sedan har även en känslighetsanalys utförts på elektrolysörerna. Potentialen att generera värme beror på typen av elektrolysör där AWE genererar 77 MWh restvärme per dygn och PEM genererar potentiellt 67 MWh restvärme per dygn. Vidare behöver AWE 64 kWh el för att producera 1 kg vätgas medan PEM behöver 66,5 kWh el per producerat kg vätgas. Intäkterna från restvärmeförsäljningen för AWE beräknades årligen till ungefär 7mnSEK och för PEM ungefär 6 mnSEK. För att elektrolysframställd syrgas ska kunna konkurrera med kryogent framställd syrgas bör inte priset övergå 108 SEK/ton. För 10 MW elektrolysören beräknas syrgasförsäljningen kunna inbringa omkring 1,1 mnSEK årligen både för AWE och PEM. Totala inkomsten för AWE blir drygt 8,1 mnSEK/år och 7,1 mnSEK/år för PEM. AWE processen är att föredra då den är mer ekonomiskt hållbar då inkomsten från biprodukterna är 12% högre än PEM på grund av högre produktion av syrgas samt större generering av restvärme.