Catalisadores de Ni (10% em massa) suportado em matrizes mistas MgO-SiO2 foram aplicados na reação de reforma a vapor de glicerol. Os efeitos do teor de MgO como aditivo e do método de preparação foram avaliados frente às propriedades físico-químicas e texturais dos materiais; assim como à atividade, seletividade, estabilidade e formação de carbono na reforma a vapor do glicerol. Os catalisadores foram preparados com diferentes teores mássicos de MgO (10%, 30% e 50%) sobre SiO2 comercial, utilizando processo via seca (mistura física) e via úmida (impregnação sequencial com diferentes solventes: água, etanol e acetona). Foram utilizadas as técnicas de caracterização de espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, termogravimetria, difratometria de raios X in situ com O2, redução a temperatura programada com H2, difratometria de raios X in situ com H2, dessorção a temperatura programada com H2 e microscopia eletrônica de varredura. Foi observado que o Ni(II) interage de forma variada com os suportes com diferentes teores de MgO, e que a polaridade do solvente de impregnação utilizado no processo de preparação influencia as propriedades dos catalisadores. A fim de verificar a atividade, seletividade e deposição de carbono; os catalisadores foram testados na reação de reforma a vapor de glicerol a 600oC, por um período de 5h e razão molar água:glicerol de 12:1. Após as reações, os catalisadores foram novamente submetidos às análises de termogravimetria, difratometria de raios X e microscopia eletrônica de varredura, visando a caracterização dos depósitos de carbono obtidos durante o processo catalítico. Os catalisadores de matrizes mistas se mostraram ativos e apresentaram seletividades similares para os produtos gasosos CH4, CO e CO2, além de um alto rendimento em H2. Observou-se que a adição de MgO no suporte, aumentou a dispersão do Ni(II) no material, que por sua vez, influenciou na quantidade de carbono depositado ao longo da reação. A polaridade do solvente de impregnação também teve influência na dispersão metálica, sendo que, quanto menor a polaridade do solvente, maior foi a dispersão obtida no catalisador, e menor a deposição de carbono na reação. O material que apresentou o melhor desempenho catalítico frente ao rendimento de H2 e à deposição de carbono, foi o catalisador preparado com 30% de MgO com etanol como solvente de impregnação. / Ni catalysts (10wt%) supported on MgO-SiO2 were assessed in glycerol steam reforming reaction. The effects of MgO as additive and preparation method were evaluated on physico-chemical and textural materials properties; as their activity, selectivity, stability and carbon formation in glycerol steam reforming. The catalysts were prepared with different amounts of MgO (10wt%, 30wt% and 50wt%) on commercial SiO2 by dry process (physical mixture) and wet process (sequential impregnation with water, ethanol and acetone as solvents). Samples were characterized by energy dispersive X-ray spectroscopy, nitrogen physisorption, X-ray diffraction, thermogravimetry, in situ X-ray diffraction with O2, temperature programmed reduction with H2, in situ X-ray diffraction with H2, temperature programmed desorption with H2 and scanning electron microscopy. It was observed that the Ni(II) interacts differently with supports with different MgO content, and the polarity of impregnation solvent used in preparation process influences on catalysts properties. In order to evaluated the activity, selectivity and carbon deposition, the catalysts were tested in glycerol steam reforming reaction at 600oC for 5h and water:glycerol molar ratio of 12:1. After reaction, carbon deposits obtained during the catalytic process were characterized by thermogravimetry, X-ray diffraction and scanning electron microscopy. Mixed matrices catalysts were active in glycerol steam reforming and showed similar selectivity for the gaseous products (H2, CH4, CO and CO2), with a high H2 yield. It was observed that the addition of MgO increased Ni(II) dispersion on material, which influenced on the quantity of carbon deposited during reaction. Polarity of impregnation solvent had also influence on metallic dispersion, and smaller the solvent polarity, higher the dispersion obtained in the catalyst, and lower the carbon deposition on reaction. The material that showed the best catalytic performance in H2 yield and carbon deposition, was the catalyst prepared with 30wt% of MgO with ethanol as impregnation solvent.

A crescente busca por fontes alternativas de energia tem despertado o interesse no uso do hidrogênio e do gás de síntese obtidos a partir de fontes renováveis. Dentre essas fontes destacam-se o etanol, produzido no Brasil a partir da cana-de-açúcar e com uma rede de abastecimento já desenvolvida, e o glicerol, obtido como subproduto na produção do biodiesel. Hidrogênio e gás de síntese podem ser obtidos a partir da reação de reforma a vapor de etanol e glicerol (RVE e RVG), levando assim a crescente interesse no desenvolvimento de catalisadores eficientes no processo de produção de H2 e gás de síntese a partir desses álcoois. <br />Na presente tese foram estudados catalisadores de níquel suportados em soluções sólidas de CexZr1-xO2, visando avaliar o desempenho dos mesmos nas reações de RVE e RVG. Os suportes foram preparados através do método Pechini e os catalisadores foram preparados por impregnação e polimerização em única etapa, variando-se o teor metálico em 5, 10 e 15% em massa. Sobre o catalisador com melhor desempenho catalítico foram adicionados, por impregnação, os seguintes metais nobres (promotores): Rh, Ru, Pt e Au (1% em massa). <br />Os suportes e catalisadores foram caracterizados por difração de Raios X (DRX); espectroscopia Raman, redução a temperatura programada com H2 (RTP H2), capacidade de estocagem de oxigênio (OSC); fisissorção de N2 (método B.E.T.); espectroscopia na região do infravermelho com reflectância difusa com CO (DRIFTS - CO), espectrocospia de absorção de Raios X (XAS - XANES RTP-H2), espectroscopia fotoeletrônica de raios X (XPS), espectroscopia dispersiva de Raios X (EDX) e microscopia eletrônica de varredura (MEV). <br />Os ensaios catalíticos foram realizados nas temperaturas de 600 e 700&deg;C para a RVG e a 400, 500 e 600&deg;C para a RVE, utilizando uma razão água:álcool de 3:1. Foram realizados também análises de DRIFTS acoplado a um espectrômetro de massas visando identificar os intermediários formados durante a reação de RVE. A partir dos ensaios catalíticos observou-se que a composição do suporte, o teor metálico e o método de preparação influenciam na seletividade em produtos gasosos devido a mudanças estruturais causadas, principalmente na dispersão da fase ativa sobre o suporte. Além disso, observou-se que a adição de metais nobres favoreceu uma menor deposição de carbono sobre os catalisadores. / The growing interest for alternative energy sources has stimulated the interest in the use of hydrogen and syngas obtained from renewable sources. Among these sources, the use of ethanol produced in Brazil from sugar cane and with a supply network already developed, and glycerol obtained as a byproduct in the biodiesel production have been highlighted in the last years. <br />Hydrogen and syngas can be produced from steam reforming of ethanol and glycerol reactions (SRE and SRG), leading to a growing interest in the development of efficient catalysts for the production of H2 and syngas from these alcohols. <br />In the present thesis, catalysts of nickel supported on CexZr1-xO2 solid solution were studied, with the goal of evaluating the performance of those in the SRE and SRG reactions. The supports were prepared by Pechini method and the catalysts were synthesized by impregnation and polymerization method in one step, with nickel loads of 5 wt.%, 10 wt.% and 15 wt.%. On the catalyst with better catalytic performance, it was impregnated 1wt% of Rh, Ru, Pt or Au as promoter. <br />Supports and catalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, temperature-programmed reduction (TPR), oxygen storage capacity (OSC), N2 physisorption (B.E.T. method), Diffuse Reflectance Infrared Spectroscopy with CO (DRIFTS - CO), X-ray absorption near edge structure (XANES - TPR H2), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX) and Scanning electron microscopy (SEM). <br />The catalytic tests of SRG were performed at 600 and 700&deg;C and for SRE at the tests were carried out at 400, 500 and 600&deg;C. The feed of water:alcohol was in the molar ratio of 3:1. DRIFTS coupled to a mass spectrometer analyzes was also carried out to identify the intermediates formed during the SRE. From the catalytic tests it was possible to observe that the support composition, metal load and preparation method influenced the selectivity to gaseous products, probably due to structural changes caused, mainly in the dispersion of the active phase on the support. Also, it was observed that the addition of noble metals favored a lower carbon deposition on the catalysts.

No description available.

Les trois familles catalytiques à base de perovskites contenant du Ni: massives [[LnFe1-x-yNiyMxO3-δ] (Ln=La, Pr; B=Co, Mn, Ru), sur support [mLnNi0.9Ru0.1О3/nMg-γ-Al2O3] (Ln = La, Pr) et structuré [mLaNi0.9Ru0.1О3/nMg-γ-Al2O3/mousses structurées] ont été synthétisés, caractérisés et testés dans les réactions de vaporeformage de l'éthanol et de glycérol. Les effets de la composition chimique et de la méthode de synthèse sur les propriétés structurelles et texturales, ainsi que sur la réductibilité des échantillons initiaux ont été évalués. L'utilisation préférentielle de Pr, Ni et Ru dans la composition de catalyseur a été démontrée pour toutes les familles. Le rôle essentiel de la modification du support γ-Al2O3 avec ≥ 10%mass de Mg introduit par imprégnation humide pour le catalyseur supporté a également été prouvé. Des catalyseurs de la composition optimale fournissant une activité élevée dans le vaporeformage de l'éthanol et du glycérol à T = 650 °C ont été trouvés: le meilleur catalyseur massif à base du précurseur PrFe0.6Ni0.3Ru0.1O3 fournit une activité élevée pendant au moins 7 h, grâce à la facilité de leur réduction et les propriétés d'oxydoréduction de l'oxyde de praséodyme formé. Les catalyseurs sur support 10-20% PrNi0.9Ru0.1O3/10-15%Mg-γ-Al2O3 fournissent le meilleur rendement en hydrogène (~ 90%) et la stabilité pendant ~ 20 heures. Le catalyseur structuré optimisé à base de la plaquette Ni-Al métallique fournit le rendement stable en hydrogène 80-87% dans l’oxy-vaporeformage d'éthanol dans les mélanges concentrés (concentration d'éthanol de 30%) dans un réacteur pilote pendant 40 heures. Les résultats obtenus rendent ces systèmes catalytiques structurés très prometteurs à utiliser dans les générateurs électrochimiques à base de piles à combustible avec l'utilisation de ressources renouvelables peu coûteuses comme bio-huile. / The three catalytic families based on Ni-containing perovskites: massive [LnFe1-x-yNiyMxO3-δ] (Ln=La, Pr; B=Co, Mn, Ru), supported [mLnNi0.9Ru0.1О3/nMg-γ-Al2O3] (Ln = La, Pr) and structured [mLaNi0.9Ru0.1О3/nMg-γ-Al2O3/structured foams] were synthesized, characterized and tested in the reactions of the ethanol and glycerol steam reforming. The effects of the chemical composition and synthesis method on the structural and textural properties, as well as on reducibility of initial samples were evaluated. The preferred use of Pr, Ni and Ru in the catalyst composition was shown for all families. The essential role of the effective γ-Al2O3 support modification with the ≥10 % wt. of Mg introduced by wetness impregnation for the supported catalyst was also proved. Catalysts of the optimal composition providing a high activity in steam reforming of both ethanol and glycerol at T= 650 °С were found: the best massive catalyst based on the PrFe0.6Ni0.3Ru0.1O3 precursor provides high activity for at least 7 hours, which is explained by the ease of their reduction and the oxidation-reduction properties of the praseodymium oxide formed. Supported 10-20% PrNi0.9Ru0.1O3/10-15%Mg-γ-Al2O3 provide the greatest yield of hydrogen (~ 90%) and stability for ~ 20 hours. Structured catalyst based on the metal Ni-Al platelet provides the yield of hydrogen 80-87% in oxy-steam and steam reforming of ethanol in the concentrated mixtures (ethanol concentration of 30%) in a pilot reactor for 40 hours. The results obtained make these structured catalytic systems very promising to use in electrochemical generators based on fuel cells with the use of inexpensive renewable resource – bio-oil.

<p>Fuel cell propulsion systems fueled directly with hydrogen are being seriously considered as a means of powering future light-duty vehicles. One of the greatest impediments to the introduction of such vehicles is the perception that transitional infrastructure to supply hydrogen will be an insurmountable obstacle. This transitional infrastructure requirement might be met through the introduction of very small scale refueling appliances which provide compressed hydrogen for either one vehicle or a small fleet of vehicles. These small appliances must be efficient, non-polluting and low in cost.</p> <p> The report investigates the feasibility of one type of refueling appliance based upon chemical reformation of natural gas in a steam reformation process. A natural gas steam reformer employing a palladium-alloy membrane hydrogen separator operated at high pressure and temperature (15+ bar and about 1200 K), should attain a net system efficiency between 60% and 80% (LHV).</p> <p> Initial kinetic modeling of the reformer suggested that for mono-tubular reactor geometries the reactor was heat transfer limited. Thus, parallel micro-tubular or plate-frame geometries might yield the highest space velocity. Critical issues which must be resolved include required degree of hydrogen recycle for catalyst stability as well as the catalyst-specific kinetics. <p> Reforming of natural gas to hydrogen appears to be a viable option for very small scale hydrogen refueling appliances. A good deal of experimental and analytical design work is required to develop such systems, but they should meet the important requirements for this application.</p> / Master of Engineering

Awareness of the climate situation and greenhouse gas emissions from fossil fuels has focused attention on hydrogen as a renewable and sustainable energy resource. In this work an economic analysis of hydrogen production by a photovoltaic electrolysis system was conducted. Equations and solution methods from previous works [1, 2] have been used to compile the results. In order to run the electrolysis of water, electricity from the photovoltaic system was used. The photovoltaic electrolysis system for this analysis has been sized with data from previous works [3, 4] to satisfy the hydrogen consumption for a fuel cell bus. Annual savings, payback time and production costs of hydrogen and electricity were compared to analyses conducted by Paolo Laranci [1] and Lucia Bollini Braga [2]. CO2 emissions from steam reforming of natural gas and sugar cane bagasse ethanol have been calculated. In addition ethics for using natural gas and sugar cane bagasse for fuel production was studied to determine the advantages and disadvantages for respective hydrogen production processes. The estimated production cost for photovoltaic electricity calculated in this thesis was higher than the result achieved in Larancis [1] work. In addition the production cost was higher than for electricity from hydropower and photovoltaic-systems in Latin America [2] and also than for the electricity tariff in Brazil [1]. Payback time and annual savings calculated in this thesis was found to be higher than for Larancis photovoltaic system. To reduce the production cost solar cells with higher efficiency should be used, investments costs for the system reduced and governmental subsidies raised. The estimated production cost for photovoltaic electrolysis hydrogen calculated in this thesis was higher compared to Lucia Bollini Braga's. The production cost for hydrogen by steam reforming of natural gas and sugar cane bagasse ethanol was also an economically favorable alternative. For hydrogen produced by photovoltaic electrolysis to be an economically advantageous alternative the electrolysis operating hours should increase likewise the electrolyser efficiency. In addition the investment cost for the electrolyser should decrease. By using photovoltaic electrolysis to produce hydrogen fossil CO2-emissions are eliminated and abundant solar energy can be utilized. Brazil is a country that possesses great natural resources of sugar cane bagasse. Steam reforming of ethanol from sugar cane bagasse could be a future option for producing sustainable, economically favorable and ethically acceptable hydrogen in Brazil. / Medvetenheten om klimatsituationen och utsläppen av växthusgaser från fossila bränslen har riktat uppmärksamheten mot vätgas som är en förnybar och hållbar energiresurs. I detta arbete har en ekonomisk analys för produktion av vätgas genom fotovoltaisk elektrolys av vatten genomförts. Ekvationer och lösningsmetoder från tidigare arbeten [1, 2] har använts för att sammanställa resultat. För att driva elektrolysen av vatten används elektricitet från det fotovoltaiska systemet. Systemet för denna analys har dimensionerats med hjälp av data från tidigare arbeten [3, 4] för att satisfiera konsumtionen av vätgas för en bränslecellsbuss. Årliga besparingar, payback och produktionskostnader för vätgas och elektricitet har jämförts med analyser utförda av Paolo Laranci [1] och Lucia Bollini Braga [2]. Koldioxidutsläpp för ångreformering av naturgas och etanol från sockerrörs bagass har beräknats. Utöver detta har en etikstudie för användning av naturgas och etanol (ur sockerrörs bagass) vid bränsleproduktion gjorts för att avgöra fördelar och nackdelar med respektive system för vätgasproduktion. Den i detta arbete beräknade produktionskostnaden för elektricitet från det fotovoltaiska systemet var högre än resultatet som åstadkoms i Larancis [1] arbete. Vidare var den i detta arbete beräknade produktionskostnaden högre än för elektricitet från vattenkraft och fotovoltaisk energi i Latinamerika [2] samt elpriset i Brasilien[1]. Payback-tiden och de årliga besparingarna visade sig vara högre för det fotovoltaiska systemet beräknat i denna analys än för Larancis system. För att minska produktionskostnaderna bör solceller med högre verkningsgrad användas, investeringskostnader av fotovoltaiska system minskas och statliga subventioner för installationen ökas. Den i detta arbete beräknade produktionskostnaden för vätgas genom fotovoltaisk elektrolys var högre jämfört med Lucia Bollini Bragas system. Produktionskostnaden för vätgas genom ångreformering av naturgas och etanol (ur sockerrörs bagass) var likaså ett mer ekonomiskt gynnsamt alternativ än fotovoltaisk elektrolys. För att vätgas producerat genom fotovoltaiskt elektrolys ska vara ekonomiskt fördelaktigt bör elektrolysens drifttimmar ökas, elektrolysen verkningsgrad öka och investeringskostnader för elektrolysen minska. Genom att använda fotovoltaisk elektrolys för att framställa vätgas elimineras fossila CO2-utsläpp och solenergi som finns i stort överskott kan utnyttjas. Brasilien är ett land som besitter stora naturresurser i form av sockerrör. Ångreformering av etanol från sockerrörs bagass kan vara ett framtida alternativ för att framställa hållbar, ekonomiskt gynnsam och etiskt accepterad vätgas i Brasilien.

In the present work it is evaluated the possibility of incorporating the production of hydrogen through the steam reforming of ethanol in a sugar-alcohol plant. The analysis is made using as a model an existing plant located in São Paulo, the Pioneros Distillery. An energetic and exergetic analysis is performed. Three operating scenarios were analyzed. In the first configuration the plant only generates electricity to supply its internal needs. In a second scenario the plant uses all the bagasse to generate electricity, targeting to sell electric power. Finally it was considered the possibility to incorporate the hydrogen production by ethanol steam reforming. The capacity of the plant to produce hydrogen is evaluated. The surplus bagasse is used to generate the electricity and thermal energy required for hydrogen production. A part of the anhydrous alcohol is used in the reformer for hydrogen production. An energetic study of the plant is developed based on the first law of thermodynamics. Some important parameters related to the thermal system performance are evaluated like: steam consumption in the process, specific consumption of steam turbines; and those properly related to plants of sugar-ethanol sector as: electrical or mechanical power generated from one ton of sugarcane and power generated from a given amount of bagasse burned in the boiler. It is considered the possibility of generating electricity using bagasse, which could be sold to the local energy concessionaire. Characteristic parameters of a cogeneration system (α and β) are also evaluated, these parameters depend on the characteristics of the thermodynamic system and the operating strategy. The system energy losses, excluding those located in the boiler and the electric generator, are higher in scenario 2 than in scenario 1. The efficiency is 70% in Scenario 1 and 57% in scenario 2. In scenario 3, the plant's potential for hydrogen generation is 4,467,000Nm3/year (951Nm3/h). To achieve this, the new process uses 7 % of the anhydrous ethanol produced in the plant, which implies a surplus of 37 lethanolanhydro/tcane available for sale. In this configuration all the bagasse is used for electricity and heat generation required for the hydrogen production. The hydrogen could be used for fuel cell vehicles. The plant is able to supply 68 buses with autonomy of 200 to 300 km per day. The incorporation of the hydrogen production process by steam reforming represents an attractive alternative to the sugar-alcohol sector.

This work aims an ecological and exergetic analysis of the hydrogen production by steam reforming of part of the ethanol produced in a sugar-ethanol plant. The Pioneiros Distillery, located in São Paulo, is used as model for this study. Three cases are described. In case 1 the plant produces energy only for domestic needs. A part of bagasse is not burned and it is stored. In Case 2, all available bagasse is used for production of steam. Part of the steam is used in the production process meeting the demand of the plant and the rest of steam is converted into electrical energy that can be sold at concessionaires. In Case 2 it is produced more energy than in Case 1. Case 3 includes the production of hydrogen by steam reforming of a part of the produced ethanol. Steam and energy for steam reforming is generated from combustion of bagasse. An exergetic analysis is performed. The exergy flows associated with the sugar-ethanol plant are calculated locating and quantifying the losses and irreversibility.  The ecological impact of use of the bagasse as fuel to generate thermal and electrical energy for the ethanol reformer was studied. The main pollutants that damage the atmosphere, namely: CO, CO2, NOx and PM have been taking into account. Carbon Dioxide emissions were calculated taking into account the carbon cycle (considering the absorption of carbon dioxide by the sugarcane during its growth), resulting in negative balance emissions, i.e., carbon dioxide was absorbed in higher amounts than emitted. The thermodynamics (ηsystem) and ecological (ε) efficiencies of Steam reforming of ethanol were calculated. The thermodynamic efficiency was 56% and the ecological efficiency was 80%. When the carbon cycle is taking into account the ecological efficiency is 90%. The incorporation of an ethanol reformer in a sugar-ethanol plant for hydrogen production is a very interesting option where environmental benefits are obtained. Problems related with the storage of bagasse are avoided because all the bagasse is burned for the production of steam and energy to the reformer. The amount of hydrogen that can be produced in Pioneiros Distillery could supply fuel for 68 buses with a range from 200 to 300 km per day.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24106号 / 工博第5028号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

This work presents a techno-economic analysis of multiple direct hydrogen production technologies using different blends of Arabian crude oil and natural gas as feedstock: Auto thermal reforming, steam reforming, and combined reforming technologies are thermodynamically and technically evaluated through development of process flowsheets. Comparative analysis indicates that combined reforming using Arabian light crude oil achieves a 22.69 % of hydrogen recovery with carbon capture, which is higher than auto thermal reforming and steam reforming by 0.7 %. At the same time, auto thermal reforming achieves a 26.70 % of hydrogen recovery without carbon capture, which is higher than steam reforming and combined reforming by 4 %. Arabian heavy, medium, light, and extra light are evaluated using auto thermal reforming technology to estimate hydrogen recovery values. A wide range of crude oil and natural gas prices are included in the analysis to calculate hydrogen production cost. With crude oil price at 90 USD/bb, the hydrogen production cost is 2.9 USD/kg, and natural gas prices at 30 USD/MMBtu (Europe), 20 USD/MMBtu (Japan), and 2.5 USD/MMBtu (GCC region), the hydrogen production cost is 4.5, 3.0, and 0.4 USD/kg respectively.