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.

The reaction barrier and heat of formation of the various dehydrogenation reactions involved in the steam reforming of ethane is a critical concern in the applications and understanding of these reactions. Focusing on Ir-based catalyst, we report a comprehensive reaction network of dehydrogenation of ethane on Ir(100) based on extensive density functional theory calculations performed on 10 C-H bond cleavage reactions, utilizing the Vienna Ab Initio Package codes. The geometric and electronic structures of the adsorption of C2Hx species with corresponding transition-state structures is reported. We found that the C-H bond in CH3C required the most energy to activate, due to the most stable four-fold hollow adsorption site configuration. Ethane can easily dissociate to CH3CH and CH2CH2 on Ir(100) and further investigation of surface temperature dependence will contribute to the research effort in this area. By using the degree of dehydrogenation of the reactant species as a variable to correlate the C-H bond cleavage barrier as well as reaction energy. DFT studies reveal that the surface Ir(100) to a great extent promotes ethane dehydrogenation when compared to other surfaces.

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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.

This dissertation describes the preparation of a novel inorganic membrane for hydrogen permeation and its application in a membrane reactor for the study of the methane steam reforming reaction. The investigations include both experimental studies of the membrane permeation mechanism and theoretical modeling of mass transfer through the membrane and simulation of the membrane reactor with 1-D and 2-D models. A hydrothermally stable and hydrogen selective membrane composed of silica and alumina was successfully prepared on a macroporous alumina support by chemical vapor deposition in an inert atmosphere at high temperature. Before the deposition of the silica-alumina composite, multiple graded layers of alumina were coated on the alumina support with a mean pore size of 100 nm by the sequential application of three boehmite sols with gradually decreasing sol particle sizes of 630, 200 and 40 nm, respectively. The resulting supported composite alumina-silica membrane had high permeability for hydrogen in the order of 10-7 mol m-2 s-1 Pa-1 at 873 K with a H2 /CH4 selectivity of 940 and exhibited much higher stability to water vapor at the high temperature of 873 K. In addition, the same unusual permeance order of Heï¼ H2ï¼ Ne previously observed for the pure silica membrane was also observed for the alumina-silica membrane, indicating that the silica structure did not change much after introduction of the alumina. The permeation of hydrogen and helium through vitreous glass and silica membranes was modeled using ab initio density functional calculations. Comparison of the calculated activation energies to those reported for vitreous glass (20—40 kJ mol -1) indicated the presence of 5- and 6-membered siloxane rings, consistent with the accepted structure of glass as a disordered form of cristobalite. The experimental studies of the steam reforming of methane were examined at various temperatures (773-923 K) and pressures (1-20 atm) with a commercial Ni/MgAl2O4 catalyst in a hydrogen selective silica-alumina membrane reactor and compared with a packed bed reactor. One-dimensional and two-dimensional modeling of the membrane rector and the packed bed reactor were performed at the same conditions and their performances were compared with the values obtained in the experimental study. Improved methane conversions and hydrogen yields were obtained in the membrane reactor compared to the packed bed reactor at all temperatures and pressures. From the two modeling studies, it was also found out that the two-dimensional model performed better in the membrane reactor case especially at higher pressures. / 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.

Deactivation of catalysts were investigated focusing on three industrial processes: 1) Selective Catalytic Reduction (SCR) for abatement of NOx from biomass combustion using V2O5-WO3 /TiO2 catalysts; 2) Catalytic oxidation of volatile organic compounds (VOC) from printing industries using a Pt/γ-Al2O3 catalyst; and 3) Ni and Pt/Rh catalysts used in steam reforming reaction of bio-syngas obtained from biomass gasification. The aim has been to simulate industrial conditions in laboratory experiments in order to comprehend influence of compounds affecting catalysts performance. Typical catalyst lifetimes in industrial processes are several years, which are a challenge when accelerating deactivation in laboratory scale experiments where possible exposure times are few hours or days. Catalysts can be introduced to deactivating compounds through different routes. The first method examined was gaseous exposure, which was applied to deactivate VOC oxidation catalyst through exposure of gaseous hexamethyldisiloxane. The second method involved wet impregnation and was used for impregnation of SCR catalyst with salt solutions. The third method was based on exposure and deposition of size selected particles of deactivating substances on the catalyst. The latter device was developed during this work. It was applied to monolithic SCR catalysts as well as to pellet catalysts intended for steam reforming of biomass gasification syngas. Deactivated SCR catalyst samples by size selected exposure method were verified and compared with SCR catalysts used in a commercial biomass boiler for 6 500 h. Evaluations of fresh and deactivated samples were investigated using BET surface area; chemisorption and temperature programmed desorption (TPD); surface morphology using Scanning Electron Microscopy (SEM) and poison penetration profile through SEM with an Electron Micro Probe Analyser (EMPA) also equipped with a energy dispersive spectrometer (EDS); chemical analysis of accumulation of exposed compounds by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES); and influence on catalyst performance. The size selected generated particles of deactivating substances were characterized with respect to mean diameter and number size distribution through Scanning Mobility Particle Sizer (SMPS) and mass size distribution applying an Electric Low Pressure Impactor (ELPI). Results from catalyst characterization methods were useful tools in evaluation of catalyst deactivation routes. Understanding deactivation processes and impact on catalyst performance is vital for further optimization of catalysts with respect to performance and lifetime. Further research in this field can provide more resistant catalysts for application in industry leading to higher commercial benefits and further application of environmental catalysts in thermo-chemical conversion of biomass.

Chemical reactions can have a staggering amount of molecular complexity. Reaction mechanisms have been proposed with over one hundred elementary reaction steps that occur in the same system simultaneously. While several methods exist to simplify and make sense of the pathways and kinetics via which these reactions proceed, e.g., reaction graphs, sensitivity or flux analysis, microkinetic analysis, and comparison of energy landscapes, etc., these methods all have limitations and are often not able to capture a comprehensive picture of the kinetics of system. It has been found useful to view these mechanisms as a network, i.e., a reaction graph. These graphs enable the visualization of the pathways of the reaction and can provide an analytical tool for pathway and kinetic analysis. However, many of the specific graph-theoretic approaches in the literature are not the most suitable for kinetic analysis of complex mechanisms; as they are simply not based on rules that are rigorous enough to fully enumerate all the pathways or provide quantitative analysis of the reaction rates. Our Reaction Route (RR) Graph approach is different in that it depicts the mechanism by a graph that is consistent with all physical and chemical laws associated with reaction networks, particularly being consistent with mass and energy conservation, i.e., Kirchoff’s Flux Law (KFL) and Kirchoff’s Potential Law (KPL). Because of their adherence to these laws, RR Graphs are able to provide an accurate graph-theoretical tool not only for depicting all reactions routes as walks (hence the name RR Graph) but also for pruning mechanisms and allowing a simplified but accurate quantitative description of reaction rates. This adherence to KFL and KPL does mean that the construction and implementation of these graphs can be prohibitively difficult for large mechanisms. For large reaction systems,especially nonlinear mechanisms, it is not realistic to generate these graphs by hand. And although there exists an analytical solution to find a determinant matrix for the RR Graph of a mechanism, the process involves an exhaustive search for a solution which experiences a combinatorial explosion as the number of steps gets very large. This leads to the idea of developing an algorithm for a computer program that can determine how to generate these graphs automatically. Unfortunately, the same combinatorial explosion is present such that for a moderately sized twenty step mechanism, it could take an average computational processor over a decade to find a solution. We have determined, however, that this brute force combinatorial approach can be avoided if heuristics could be developed to bridge gaps in our knowledge of how these graphs are constructed. Thus, developing a better analytical approach and/or a tighter set of heuristics for a computer algorithm are the overarching goals of this work. To make progress toward developing such heuristics, a set of microkinetic mechanisms were analyzed with the notion that the realization of the RR Graphs would highlight a better approach to their construction and usage. In particular, a very large linear reaction system, a smaller linear system and two non-linear reaction systems were analyzed to develop insights into how each graph is manually constructed and analyzed. Furthermore, kinetic analysis was done for these mechanisms and compared to experimental data and other analytical tools to prove not only the validity of the RR Graphs, but also how they are a significant improvement over more commonly used approaches for mechanistic and kinetic analysis. Based on the lessons learned through a consideration of these examples, a set of heuristics are established and enumerated with the ultimate goal of developing an intuitive algorithm that can help automate drawing and kinetic analysis via RR Graphs of complex mechanisms.

Dans le but d'étudier la production d'hydrogène via la réaction de vaporeformage catalytique du méthanol et de déterminer les différents paramètres influençant la réaction, la performance des catalyseurs Cu-Zn/CeO₂-Al₂O₃ a été évaluée. L'imprégnation du cuivre sur la cérine ou l'alumine, montre de meilleurs performances catalytiques que le zinc imprégné sur ces mêmes supports. En présence de la cérine, l'activité a été liée à la dispersion des espèces Cu²⁺ isolés en interaction avec la matrice, qui se réduisent dans la phase de prétraitement du catalyseur. En présence de l'alumine, des espèces spinelles CuAl₂O₄ très stables et non réduites ont été formées rendant les catalyseurs moins actifs. Concernant les catalyseurs à base de cuivre imprégné sur l'oxyde mixte 10Ce10Al, la présence de l'alumine a favorisé la dispersion de la cérine à sa surface améliorant ainsi l'échange d'oxygène entre la phase active et le support sans marquer une influence sur l'espèce active. Les agglomérats de CuO formés sur les catalyseurs à forte teneur en cuivre ont contribué à la diminution de formation de sous produits durant la réaction. L'effet promoteur du zinc a été révélé en stabilisant le cuivre réduit au cours du test sous forme d'espèces Cu⁺ qui sont les plus actives dans la réaction de vaporeformage du méthanol. Tous les catalyseurs à base de cuivre n'ont révélé aucune présence de coke à leur surface, contrairement aux catalyseurs à base de zinc où des espèces carbonées ont été identifiées. La désactivation du catalyseur avec le temps a été attribuée à la formation de ces espèces, qui bloquent l'accessibilité des sites actifs du catalyseur. / In order to study the hydrogen production via the catalytic steam reforming of methanol and to determine the influence of different parameter on this reaction, the performance of the Cu-Zn/CeO₂-Al₂O₃ catalysts was evaluated. The impregnation of copper over ceria or alumina has shown better catalytic performance than the impregnation of the zinc on the same supports. In the presence of ceria, the catalytic activity has been related to the dispersion of isolated Cu²⁺ species in interaction with the matrix, which were reduced during the pre-treatment phase of the catalyst. In the presence of alumina, stable and unreduced CuAl₂O₄ spinal species were formed, leading to a lower catalytic activity. Concerning the copper based catalysts impregnated on 10Ce10Al mixed oxide, the presence of alumina has promoted the dispersion of the ceria that enhances the oxygen exchange between the active phase and the support without influencing the active phase. The agglomerated CuO species formed in the catalysts with the high copper content have contributed to lower the by-product formation during the reaction. The promoter effect of the zinc was revealed by the stabilisation of the reduced copper into Cu⁺ species that are the most active species in the steam reforming of methanol reaction. No coke formation was revealed on the copper based catalysts, unlike the zinc based catalysts where carbon species were identified. The catalytic deactivation with time on stream was attributed to the formation of those species that blocks the accessibility of the catalytic active sites.