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.

The subject of this dissertation is advanced inorganic membranes and their application in membrane reactors (MRs). The reaction studied is the ethanol steam reforming (ESR) reaction using Co-Na/ZnO catalysts, chosen because of their high activity and stability. The Co-Na/ZnO catalysts were prepared by a co-precipitation method and it was found that promotion with a moderate amount of Na (1.0 wt%) produced a catalyst with stable ethanol conversion and product selectivity. Higher cobalt loading, higher W:E ratio, higher reaction temperature, and lower space velocity enhanced the conversion of ethanol to H2 and CO2 while reducing the formation of undesirable acetaldehyde. Acetaldehyde was a primary product of the ESR reaction. Studies of the effect of hydrogen permeance on the ESR reaction at 623 K were performed in MRs equipped with silica-based and palladium-based membranes of different hydrogen permeances, and the highest ethanol conversion enhancement of 44 % and hydrogen molar flow enhancement of 69 % compared to a packed-bed reactor (PBR) were obtained in a MR fitted with a membrane with the highest hydrogen permeance. An operability level coefficient (OLC), defined as the ratio of the hydrogen permeation and hydrogen formation rates, was suggested as a useful tool for estimating performances of MRs for different reforming reactions such as methane dry reforming (MDR), methane steam reforming (MSR), methanol steam reforming (MeSR), and ethanol steam reforming (ESR) reactions. Studies of the effect of pressure (1-10 atm) on the ESR reaction at 623 K were carried out in a PBR and a MR fitted with a Pd-Cu membrane prepared by an electroless plating of palladium and copper at 333 K. Comparison studies showed that increasing pressure in both reactors resulted in decreasing ethanol conversions and increasing hydrogen molar flows. Compared to the PBR, higher ethanol conversions and hydrogen molar flows were obtained in the MR for all pressures studied. Increasing pressure was favorable for enhancing ethanol conversion and hydrogen molar flow in the MR compared to the PBR, and the highest ethanol conversion enhancement of 48 % with the highest hydrogen molar flow enhancement of 55 % was obtained at 10 atm in the MR. / Ph. D.

Bimetallic catalysts have been widely exploited to improve the performance of various catalytic reactions. Understanding the surface properties and in particular, bimetallic interaction and support effect of the catalytic components is an important step towards rational catalyst design. In this thesis, Ni-Co thin film on polar ZnO single crystal was studied as a model catalyst for ethanol steam reforming reaction. The aim is to provide fundamental understanding of how the surface characteristics of the catalyst influence the mechanism and the efficiency of the reaction. This study focused firstly on the study of the interaction between Ni and Co in oxidative environment using Xray photoelectron spectroscopy (PES). Oxidation of Co is favoured over nickel and the surface is enriched with cobalt oxide. Secondly, Ni-Co thin film supported on polar Zn and O terminated ZnOwas studied by synchrotron based PES. The as deposited layer interacts readily with ZnO and Co is partially oxidized upon deposition, even at room temperature. The interaction of ethanol with Ni- Co/ZnO-Zn was studied by thermal desorption spectroscopy (TDS). Ethanol decomposes in different pathways on Ni and Co, in which C-C bond scission and methane production are favoured on Ni/ZnO-Zn while dehydrogenation is favoured on Co/ZnO-Zn. Finally, Ni-Co powder was studied byin-situ ambient pressure PES under reaction conditions in order to clarify the correspondence between the active state of the catalyst and the reaction activity. The product selectivity on Co catalyst is distinctly different from Ni and Ni-Co. Also, the decomposition of methyl group and the high amount of CO produced over Co is likely to be the cause for its high level of carbon deposition.

Neste trabalho foram preparados catalisadores Co/Al2O3 e Co/SiO2 por impregnação com concentração metálica entre 4,0% e 20,0% e avaliados frente às reações de reforma a vapor e reforma oxidativa de etanol, com o objetivo de avaliar a estabilidade catalítica e o rendimento em hidrogênio. Os catalisadores foram caracterizados por espectrofotometria de absorção atômica, difração de raios-X, espectroscopia Raman, redução a temperatura programada, fisissorção de nitrogênio e análise elementar de carbono. A caracterização das amostras mostrou a formação da fase Co3O4 e interações de espécies de cobalto com o suporte. Evidenciou-se que apenas os sítios de Co0 são ativos para as reações de reforma a vapor e oxidativa de etanol. A produção de hidrogênio variou de 50-70% e a de CO de 0-10%. Alta concentração metálica sobre a superfície do suporte acarretou uma baixa produção de monóxido de carbono. As reações tiveram deposições de carbono nos catalisadores variando de 2,7 a 12,7 (mg. h-1), indicando que a desativação dos materiais é devido a deposição de coque. O uso de oxigênio diminuiu a produção de coque sobre os catalisadores Co/Al2O3 e Co/SiO2. / In this work Co/Al2O3 and Co/SiO2 catalysts were prepared by impregnation with metal load between 4,0% and 20,0% and were evaluated in the reactions of ethanol steam reforming and ethanol oxidative reforming to study the catalytic stability and the hydrogen yield. Atomic absorption, X-ray powder diffraction, Raman spectroscopy, temperature programmed reduction, nitrogen fisisorption and elemental analysis of carbon were applied to describe the physical and chemical characteristics of these catalysts. The characterization of the catalysts showed the Co3O4 phase and interactions of cobalt species with the support. It was evidenced that only Co0 sites are active for the steam reforming and oxidative reforming of ethanol. The production of hydrogen was about 50-70% and CO was 0- 10%. A high metallic load gave less carbon monoxide production. In the reactions, 2,7-12,7(mg.h-1) of carbon was deposited on all catalysts, indicating that the deactivation of the materials is due to coke deposition. The use of oxygen decreases the production of carbon on the catalysts Co/Al2O3 and Co/SiO2.

Neste trabalho foram preparados catalisadores Co/Al2O3 e Co/SiO2 por impregnação com concentração metálica entre 4,0% e 20,0% e avaliados frente às reações de reforma a vapor e reforma oxidativa de etanol, com o objetivo de avaliar a estabilidade catalítica e o rendimento em hidrogênio. Os catalisadores foram caracterizados por espectrofotometria de absorção atômica, difração de raios-X, espectroscopia Raman, redução a temperatura programada, fisissorção de nitrogênio e análise elementar de carbono. A caracterização das amostras mostrou a formação da fase Co3O4 e interações de espécies de cobalto com o suporte. Evidenciou-se que apenas os sítios de Co0 são ativos para as reações de reforma a vapor e oxidativa de etanol. A produção de hidrogênio variou de 50-70% e a de CO de 0-10%. Alta concentração metálica sobre a superfície do suporte acarretou uma baixa produção de monóxido de carbono. As reações tiveram deposições de carbono nos catalisadores variando de 2,7 a 12,7 (mg. h-1), indicando que a desativação dos materiais é devido a deposição de coque. O uso de oxigênio diminuiu a produção de coque sobre os catalisadores Co/Al2O3 e Co/SiO2. / In this work Co/Al2O3 and Co/SiO2 catalysts were prepared by impregnation with metal load between 4,0% and 20,0% and were evaluated in the reactions of ethanol steam reforming and ethanol oxidative reforming to study the catalytic stability and the hydrogen yield. Atomic absorption, X-ray powder diffraction, Raman spectroscopy, temperature programmed reduction, nitrogen fisisorption and elemental analysis of carbon were applied to describe the physical and chemical characteristics of these catalysts. The characterization of the catalysts showed the Co3O4 phase and interactions of cobalt species with the support. It was evidenced that only Co0 sites are active for the steam reforming and oxidative reforming of ethanol. The production of hydrogen was about 50-70% and CO was 0- 10%. A high metallic load gave less carbon monoxide production. In the reactions, 2,7-12,7(mg.h-1) of carbon was deposited on all catalysts, indicating that the deactivation of the materials is due to coke deposition. The use of oxygen decreases the production of carbon on the catalysts Co/Al2O3 and Co/SiO2.

This thesis describes a new technique for the preparation of ultrathin Pd based membranes supported on a hollow-fiber α-alumina substrate for H₂ separation. The effectiveness of the membranes is demonstrated in the ethanol steam reforming (EtOH SR) reaction in a membrane reactor (MR) for H₂ production. The membrane preparation technique uses an electric-field to uniformly deposit Pd nanoparticle seeds on a substrate followed by deposition of Pd or Pd-Cu layers on the activated surface by electroless plating (ELP). The well distributed Pd nanoparticles allow for enhanced bonding between the selective layer and the substrate and the formation of gas tight and thermally stable Pd or Pd-Cu layers as thin as 1 µm, which is a record in the field. The best Pd membrane showed H₂ permeance as high as 5.0 × 10⁶ mol m²s⁻¹Pa⁻¹ and stable H²/N₂ selectivity of 9000 - 7000 at 733 K for 5 days. The Pd-Cu alloy membrane showed H₂ permeance of 2.5 × 10⁶ mol m⁻²s⁻¹Pa⁻¹ and H₂/N₂ selectivity of 970 at the same conditions. The reaction studies were carried out with a Co-Na/ZnO catalyst both in a packed bed reactor (PBR) and in a MR equipped with the Pd or Pd-Cu membrane to evaluate the benefits of employing membranes. For all studies, ethanol conversion and hydrogen product yields were significantly higher in the MRs compared to the PBR. Average ethanol conversion enhancement and hydrogen molar flow enhancement were measured to be 12 % and 11 % in the Pd MR and 22 % and 19 % in the Pd-Cu MR, respectively. These enhancements of the conversion and product yield can be attributed to the shift in reaction equilibria by continuous hydrogen removal by the Pd based membranes. The comparative low enhancement in the Pd MR was found to be the result of significant contamination of Pd layer by CO or carbon compounds deposition during the reaction. A one-dimensional modeling of the MR and the PBR was conducted using identical conditions and their performances were compared with the values obtained from the experimental study. The model was developed using a simplified power law and the predicted values matched experimental data with only minor deviations indicating that the model was capturing the essential physicochemical behavior of the system. Enhancements of ethanol conversion and hydrogen yield were observed to increase with rise in space velocity (SV), which could be explained by the increase in H₂ flux through the membranes with SV in the MRs. / Ph. D.

Hydrogen is considered as an alternative clean energy source due to the depletion of fossil fuels and related environmental problems. Steam reforming of bio-ethanol, has excellent potential for hydrogen production, with CO2 neutrality. Ni, Pd and Pt are the most active metals for steam reforming of ethanol. Improving catalytic activity of supported Ni catalyst by incorporating small amount of Pd or Pt is a successful method for increasing activity and stability of the catalyst. Development of active and stable catalysts with low coke formation and high hydrogen yield attracted major attention of researchers in recent decades. MCM-41 supported bimetallic mesoporous catalytic materials containing well dispersed Ni and Pd nanoballs were synthesized following an impregnation procedure. TEM images and XRD analysis of these materials indicated the formation of nickel and palladium nanoballs of 15-25 nm and 5-8 nm respectively, within the synthesized materials. These materials have quite narrow pore-size distributions in the range of 1-5 nm. In the calcined materials, nickel was in Ni+3 and Ni+2 states, however in the reduced sample most of the nickel was in Nio state, together with some NiO. Formation of NiOx crystals takes place after the calcination step. Impregnation of palladium into Ni/MCM-41 caused a decrease in the reduction temperature of NiO for about 50oC. Activity of the catalytic materials were tested in the reaction of steam reforming of ethanol.all the catalysts showed high conversion and quite high hydrogen yield over 400 oC. PdNi impregnated MCM-41 supported catalysts showed higher conversion of ethanol but lower hydrogen yield than Ni impregnated catalysts due to methane formation in the case of Pd incorporation. However, MCM-41 does not show enough hydrothermal stability for steam reforming of ethanol reaction. SBA-15 has very similar physical properties of MCM-41 with larger pores and high hydrothermal stability. Ceria also has widespread applications in catalysis area with its excellent oxygen buffering capacity. It can be used as catalyst support and also an improving agent for silica supports. Mesoporous silica SBA-15 with ordered pore structure was synthesized following a hydrothermal procedure and then bimetallic Ni-Ce and Pd-Ni-Ce incorporated mesoporous silica catalysts were prepared and tested in steam reforming of ethanol. On the other hand, ceria enriched silica structures i.e cerium/silicate composites were also synthesized. However the syntheses were unsuccessful due to the thermal sintering of ceria. Addition of ceria to the support structure decreased coke formation significantly.. According to the thermal gravimetric analysis studies conducted after ethanol steam reformin reaction at 600 oC, coke formation with Ni-SBA-15 (Ni/Si=0.10) catalyst was 40% and it was 10% with NiCe-SBA-15 (Ni/Si=0.10, Ce/Si=0.50) Activity test results obtained with Ni incorporated silica catalysts in steam reforming of ethanol gave high hydrogen yield over 4 (max. 6) and complete conversion of ethanol at 600 oC. SBA-15 found to be more stable catalyst than MCM-41 in the steam reforming of ethanol reaction. The highest hydrogen yield values were achieved by AlMCM-41 supported Ni-Ce impregnated catalysts. Aluminum in the slica matrix (3% wt.) increased the catalytic activity significantly, by giving acidic properties to the catalyst. Simultaneous and consecutive Ni and Ce impregnation were also examined. AlMCM-41 supported, consecutively Ce and Ni impregnated catalysts with Ce/Si and Ni.Si molar ratio sof 0.10, showed very high catalytic activity (5.8 at the beginning). AlMCM-41 supported catalyst were less stable because of high activity and consequently coke formation.

Les catalyseurs bimétalliques sont reconnus pour promouvoir les performances de nombreuses réactions catalytiques. Les connaissances des propriétés de surface ; notamment l’interaction entre les couches bimétalliques et le support, composants catalytiques, servent à améliorer le design des catalyseurs. Dans cette thèse, le dépôt de couches minces Ni-Co sur un monocristal ZnO a été étudié en tant que catalyseur modèle pour le vapo-réformage de l’éthanol. L’objectif du travail estd’élargir les connaissances fondamentales de l’influence des propriétés de surface (i) sur le mécanisme et (ii) sur l’efficacité de la réaction. Dans un premier temps, l’interaction entre les atomes Ni et Co sous atmosphère oxydante par spectrométrie de photoélectrons de rayons X (XPS) a été étudiée. L’oxydation du Co est favorisée ; la surface est enrichie par CoO sur Ni. Ensuite, les couches minces de Ni-Co sur monocristal polaire ZnO, possédant deux terminaisons -O et –Zn, ont été étudiées par XPS couplé à un synchrotron. L’interaction métal-support a mis en évidence que Co est oxydé dès que celui-ci est déposé à température ambiante. L’interaction entre la molécule d’éthanol et le catalyseur Ni-Co/ZnO-Zn a été étudiée par spectrométrie de masse de thermodésorption (TDS). L’éthanol se décompose par différentes voies sur Ni/ZnO-Zn et Co/ZnOZn. Ni/ZnO-Zn favorise la rupture de la liaison C-C et permet la production de méthane, tandis que Co/ZnO-Zn favorise la déshydrogénation du méthyle. Enfin, nous avons étudié le vapo-réformage de l’éthanol sur les nanopoudres de Ni-Co in-situ par XPS à pression ambiante. La sélectivité en produits sur Co est très différente de celle du Ni et Ni-Co. De plus, la déshydrogénation du méthyle et la production de CO peut entrainer la formation d’une grande quantité de carbone sur Co / Bimetallic catalysts have been widely exploited to improve the performance of various catalytic reactions. Understanding the surface properties and in particular, bimetallic interaction and support effect of the catalytic components is an important step towards rational catalyst design. In this thesis, Ni-Co thin film on polar ZnO single crystal was studied as a model catalyst for ethanol steam reforming reaction. The aim is to provide fundamental understanding of how the surface characteristics of the catalyst influence the mechanism and the efficiency of the reaction. This study focused firstly on the study of the interaction between Ni and Co in oxidative environment using Xray photoelectron spectroscopy (PES). Oxidation of Co is favoured over nickel and the surface is enriched with cobalt oxide. Secondly, Ni-Co thin film supported on polar Zn and O terminated ZnOwas studied by synchrotron based PES. The as deposited layer interacts readily with ZnO and Co is partially oxidized upon deposition, even at room temperature. The interaction of ethanol with Ni- Co/ZnO-Zn was studied by thermal desorption spectroscopy (TDS). Ethanol decomposes in different pathways on Ni and Co, in which C-C bond scission and methane production are favoured on Ni/ZnO-Zn while dehydrogenation is favoured on Co/ZnO-Zn. Finally, Ni-Co powder was studied byin-situ ambient pressure PES under reaction conditions in order to clarify the correspondence between the active state of the catalyst and the reaction activity. The product selectivity on Co catalyst is distinctly different from Ni and Ni-Co. Also, the decomposition of methyl group and the high amount of CO produced over Co is likely to be the cause for its high level of carbon deposition.

L’objectif de cette thèse de doctorat a consisté à déterminer l’influence des conditions réactionnelles du vaporeformage de l’éthanol (ESR), de la dispersion du catalyseur et de la promotion par le potassium sur l’état de la surface. Ce travail a aussi aidé à comprendre l’influence de ces facteurs sur les propriétés catalytiques. Nous avons utilisé les catalyseurs à base de cobalt (promus et non promus par le potassium) supportés à l’oxyde de cérium et à l’oxyde de zirconium à faible et à forte dispersion. Les changements de l’état de la surface des catalyseurs pendant la réaction d’ERS ont été étudiés à travers la spectrométrie photoélectronique X (XPS), alors que les changements des produits ont été analisés en utilisant la spectrométrie de masse et la chromatographie en phase gazeuse. Le catalyseur supporté sur oxyde de cérium à forte dispersion a été caractérisé sous une basse pression (0.2-20 mbar) avec le rapport molaire eau/éthanol de 3/1 (420ºC). Les autres tests ont été faits sur tous les catalyseurs sous une pression totale de 1 atm avec les rapports molaires de 3/1, 9/1, 12/1 (420ºC). Nous avons utilisé un mélange eau/éthanol dans un rapport molaire de 12/1 pour étudier les changements de l’état de la surface de tous les catalyseurs dans le temps. Il a été démontré que la sélectivité d’ESR des catalyseurs pour produire des gaz et pour déposer le carbone est réglée par la concentration des groupes hydroxyles sur la surface. Quant aux catalyseurs promus, elle dépend aussi de la concentration Kδ+–Osurfδ-. / The aim of the thesis was determination the influence of the ethanol steam reforming (ESR) reaction conditions, catalyst’s dispersion and potassium promotion on a surface’s composition and understanding the influence of these changes on catalysts’ performance. Cobalt-based catalysts (unpromoted and promoted with potassium) with low- and high-dispersed ceria and zirconia supports were used. The changes of the surface state of catalysts during the ESR were studied by means of X-ray photoelectron spectroscopy, whereas the reaction products evolution was followed by mass spectrometer or gas chromatograph. Highly-dispersed ceria-supported catalyst was characterized under low pressure conditions (0.2–20 mbar) with the water/ethanol molar ratio equal to 3/1 (at 420ºC). The other tests were carried out over all catalysts under total pressure of 1 atm with 3/1, 9/1 and 12/1 molar ratios (at 420ºC). The water/ethanol ratio of 12/1 was chosen for studies of the surface state of all catalysts with time-on-stream. It was found that the ESR selectivity to gaseous products and carbon deposition is governed mainly by surface hydroxyl species concentration; in the promoted catalysts together with Kδ+–Osurfδ- surface sites.

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