Syngas production and hydrogen separation technologies are very mature, and also extremely important for energy and chemical industries. Furthermore, these processes are the most expensive elements for many applications such as hydrogen production from renewable sources. Enhancing or intensifying these very mature technologies is very challenging, but would have tremendous impact on the performance and economics of many processes. Traditional Integrated Gasification Combined Cycle (IGCC) for syngas production need to include a carbon capture process in order to regulate their carbon dioxide emission as more and more countries and regions have implemented carbon tax policy. Integration of this process with Pd membrane has long been considered a key component to make it more feasible. With these two technologies combined together, we can produce high purity hydrogen while capturing carbon dioxide and toxic gases from the syngas product. Besides, although manufacturing the membrane reactor is expensive, after considering the carbon tax factor, it actually is more economically preferable compare with the traditional Pressure Swing Adsorption (PSA) process. Most research on Pd membrane technology has been conducted at lab scale; nonetheless, the contribution of a palladium membrane technology to economic and societal development requires its commercialization, diffusion and utilization. To generate enough incentives for commercialization, it is necessary to demonstrate the scalability and robustness of the membranes in industrial settings. Consequently, a multitube membrane module suitable for IGCC system was designed and manufactured and sent to National Carbon Capture Center (NCCC) for testing. This work developed a Computational Fluid Dynamics (CFD) model for the module and validated the model utilizing the pilot-scale experimental data generated under industrial conditions. The model was then up-scaled and used to determine the intrinsic phenomena of palladium membrane scale up. This study reveals the technical/engineering requirements for the effective design of large-scale multitube membrane modules. Mass transfer limitations and concentration polarization effects were studied quantitatively with the developed model. Methods for diminishing the concentration polarization effect were proposed and tested through the simulations such as i) increasing convective forces and ii) designing baffles to create gas recirculation. For scaled-up membrane modules, mass transfer limitation is an important parameter to consider as large modules showed severe concentration polarization effects. IGCC systems produce H2 from coal combustion; other ways of H2 production include steam-reforming processes, using natural gas or bio-ethanol as the reactant. The product contains a mixture of H2, CH4, CO, CO2 and steam. Thus, steam-reforming processes are often followed by a Pressure Swing Adsorption (PSA) unit in order to obtain pure hydrogen. Palladium membrane, on the other hand, can be integrated with steam-reforming processes and achieve the simultaneous production and purification of H2 in a single unit by reaching process intensification. Higher H2 production rate can be reached by process intensification as one of the products H2 is constantly being removed. Temperature control is a very important topic in steam reforming processes, as the reaction is overall highly endothermic; although implementing an in-unit membrane improves H2 production rate, it also makes the temperature control more difficult as the reaction equilibrium is altered by the removal of one of the products H2. Hereby, an experimental study of catalytic membrane reactor (CMR) was carried out along with both isothermal and non-isothermal CFD simulations that are validated by the experimental data in order to visualize the temperature distribution inside the reactor and understand the influence of the operating conditions including temperature, pressure and the sweep gas flow patter on the permeate side.

This thesis describes the development and characterisation of palladium optical coatings for hydrogen sensing. The main aim of the thesis was to optimise an optically interrogated palladium coated substrate to detect hydrogen at concentrations less than 1% in humid conditions (50-80%). An optical set up was constructed to investigate the change in the coatings in transmission at 650 nm on exposure to varying hydrogen concentrations in dry and wet conditions. Three different optical substrates; Polymer Optical Fibre (POF), Polymethyl methacrylate (PMMA) and glass were evaluated to determine the best support for palladium; criteria of selection were based on hydrogen detection performance in dry and humid condition (50%). PMMA was shown to be the ideal support as effect of humidity on hydrogen detection was minimal. Palladium was deposited by sputter coating technique and the coating thickness demonstrates a dependence on the deposition time and position of the substrate inside the coating chamber. The coating developed showed a response time of 1s at 5%H2, a detection range of 0-9.1% with a demonstrated detection limit of 200 parts per million (ppm) and a predicted limit of detection of 15 ppm. The rate of hydrogen detection was proposed to be diffusion limited for coating thickness up to the threshold thickness. At thicknesses less than the threshold thickness, the rate limiting step was related to the binding force between the coating and the support. The coating performance was unaffected by cross sensitive gases such as hydrogen sulphide, carbon monoxide, methane and ethene. In the presence of Relative Humidity (50-80%), the coating reached a limit of detection at 0.1% H2. However, over exposure to humidity lead to temperature effect which was compensated using a temperature compensation model developed. The surface of the coating developed was characterised by Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) and revealed that the coating developed is unaffected by the tests carried out through the PhD.

In this research it was shown that the electroless plated palladium deposited as large number of randomly oriented grains, which were separated by grain boundaries (GB). The nano-scale dimensions of these grain boundaries allowed the diffusion of helium through the palladium membrane. This implied that in a dense palladium membrane, the grain boundary network was so convoluted that helium flux could be neglected. The transmission electron microscope (TEM) images of the palladium at room temperature showed grains of about 50 nm in size and nuclei of about 5 nm in size. The TEM images of a pre-annealed Pd sample at 500ºC in hydrogen atmosphere for 48 hours, showed big grains of 100 to 200 nm in size and most of the grain boundary intersections had dihedral angles very close to 120°. However, the pre-annealed Pd sample at 500ºC in helium atmosphere for 48 hours, showed grains of the size of 70 to 100 nm and many of the grain boundary intersections did not show dihedral angles of 120°. This proved that high temperature annealing not only caused significant grain growth and grain boundary (straightening) migration, but also the grain boundary migration was faster in hydrogen than in helium atmosphere. Also, the hydrogen and helium characterization of the palladium membranes showed that the leak formed faster in hydrogen than in helium. Thus, combining the TEM observations with the membrane characterization results, it is possible to conclude that grain boundary migration is one of the most probable reasons for leak formation in palladium composite membranes. The TEM images of the pre-annealed Pd sample also showed that the grain boundaries can achieve an equilibrium configuration within 48 hours of annealing at 500°C in hydrogen. This research helped in better understanding of the role of grain boundary migration on the leak formation in the composite palladium membranes and this information can be useful for the production of leak resistant stable membranes in the future.

Yu Michael. / Thesis submitted in: July 2003. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (leaves 57-63). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Part I - --- Optimization of Palladium Catalyzed Phosphination / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Background of Phosphine Synthesis --- p.1 / Chapter 1.2 --- Preparation of Phosphines --- p.4 / Chapter Chapter 2 --- Optimization of Phosphination of Aryl Bromides / Chapter 2.1 --- Additive Effect in Phosphination of Aryl Bromides --- p.14 / Chapter 2.2 --- Iodide Effect in Phosphination of Aryl Triflate --- p.25 / Chapter 2.3 --- Low Temperature Phosphination --- p.27 / Chapter 2.4 --- Conclusion --- p.29 / Chapter Part II - --- Synthesis of Optically Active As，N Ligands and Their Metal Complexes / Chapter Chapter 1 --- 3.1 Introduction --- p.30 / Chapter Chapter 2 --- Synthesis of Optically Active As，N Ligands and Their Metal Complexes / Chapter 4.1 --- "Synthesis of As,N Oxazolines" --- p.39 / Chapter 4.2 --- "Synthesis of As,N Oxazoline Transition Metal Complexes" --- p.41 / Chapter 4.3 --- Conclusion --- p.44 / Experimental --- p.45 / References --- p.57 / Appendix --- p.64

<p>This thesis is focused on two important fields of palladium catalysis: the development of electrophilic allylic substitution reactions via bis-allylpalladium intermediates; and application of palladium pincer-complexes in the synthesis and transformations of organometallic compounds.</p><p>Palladium-catalyzed electrophilic allylation of aldehyde and imine substrates could be achieved using readily available allyl chlorides and acetates by employing hexamethylditin or bis(pinacolato)diboron reagents. The reaction proceeds under mild and neutral reaction conditions with high regioselectivity, providing the branched homoallylic products. The stereoselectivity of the reaction depends on the steric and electronic effects of the allylic substituents of the substrates. DFT modeling of the electrophilic attack on the bis-allylpalladium intermediate of the reaction revealed the origin of the regio- and stereoselectivity of the reaction.</p><p>Palladium pincer-complexes were employed as catalysts in a variety of reactions such as stannylation, selenylation, allylation, and cross coupling reactions with various electrophiles. Allylic stannylation in the presence of hexamethylditin was achieved by use of an NCN palladium pincer-complex catalyst. In contrast to the reactions catalyzed by traditional palladium catalysts, isolation of functionalized allyl stannanes was possible due to the special features of the pincer-complex catalyst. Extension of the scope of the palladium pincer-complex catalyzed electrophilic allylation reactions was achieved by using potassium trifluoro(allyl)borate instead of allyl stannanes. In addition, asymmetric electrophilic allylation of sulfonimines was achieved by employment of novel BINOL-based palladium pincer-complexes. The enantioselectivity of the pincer-complex catalyst was fine-tuned by employment of substituted analogs of BINOL.</p>

Thesis (M.S.)--Brigham Young University. Dept. of Geology, 2004. / Includes bibliographical references (p. 30-33).

This thesis is focused on two important fields of palladium catalysis: the development of electrophilic allylic substitution reactions via bis-allylpalladium intermediates; and application of palladium pincer-complexes in the synthesis and transformations of organometallic compounds. Palladium-catalyzed electrophilic allylation of aldehyde and imine substrates could be achieved using readily available allyl chlorides and acetates by employing hexamethylditin or bis(pinacolato)diboron reagents. The reaction proceeds under mild and neutral reaction conditions with high regioselectivity, providing the branched homoallylic products. The stereoselectivity of the reaction depends on the steric and electronic effects of the allylic substituents of the substrates. DFT modeling of the electrophilic attack on the bis-allylpalladium intermediate of the reaction revealed the origin of the regio- and stereoselectivity of the reaction. Palladium pincer-complexes were employed as catalysts in a variety of reactions such as stannylation, selenylation, allylation, and cross coupling reactions with various electrophiles. Allylic stannylation in the presence of hexamethylditin was achieved by use of an NCN palladium pincer-complex catalyst. In contrast to the reactions catalyzed by traditional palladium catalysts, isolation of functionalized allyl stannanes was possible due to the special features of the pincer-complex catalyst. Extension of the scope of the palladium pincer-complex catalyzed electrophilic allylation reactions was achieved by using potassium trifluoro(allyl)borate instead of allyl stannanes. In addition, asymmetric electrophilic allylation of sulfonimines was achieved by employment of novel BINOL-based palladium pincer-complexes. The enantioselectivity of the pincer-complex catalyst was fine-tuned by employment of substituted analogs of BINOL.

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This thesis focuses on the development of carbon-carbon/carbon-heteroatom bond forming reactions using strained ring systems under transition metal catalysis. The first chapter describes the use of bifunctional organoboron reagents with a rhodium catalyst to synthesize carbocycles through a cascade sequence. The reaction of norbornene derivatives gives vinylcyclopropane and cyclopentene products in moderate to good yield. The mechanistic proposal and insights into the reaction mechanism are presented. Preliminary results from studies toward an enantioselective sequential addition/cyclization process are described. The methodology is subsequently applied in the synthesis of a variety of polycyclic heteroaromatics using bifunctional heteroaryl boronate esters. The second chapter describes studies toward the formation of carbon-heteroatom bonds using cyclopropane derivatives. Under a recently developed Pd(OAc)2/PhI(OAc)2 catalytic system, methylenecyclopropanes are isomerized to substituted pyridines via a sequential fragmentation/cyclization process. Under same reaction conditions, allylic acetate products are obtained from the isomerization of cyclopropanes through a similar process.

Reaction of unsymmetrical allylic electrophiles with amines gives rise to regioisomeric allylamines. It was found that linear products result from the thermodynamically controlled isomerization of the corresponding branched products, which form initially. The isomerization was found to be promoted by the presence of acid and active palladium catalyst. The use of base shut down the isomerization pathway and allowed for the preparation and isolation of branched allylamines. This methodology provides a powerful control element, which allows for the installation of quaternary and chiral centres next to nitrogen. Later, the isomerization was combined with ring-closing metathesis to afford the synthesis of exocyclic allylamines from their thermodynamically less-stable endocyclic precursors. This rearrangement became feasible as a result of the electrophilic nature of a C – N bond in allylamines. When compared to the conventional intramolecular allylic amination, such approach escapes chemoselectivity issues, which makes it attractive attractive for late-stage synthetic modifications.