Acceptorless dehydrogenation and hydrogenation of N- and O-containing compounds on Pd3Au1(111) facets

Catalytic dehydrogenation and hydrogenation of amines and alcohols are important in the synthesis of fine chemicals. Despite several efficient homogeneous catalysts having been identified, highly active heterogeneous catalysts remain elusive, although they would meet an unmet need. Here, we show that bimetallic Pd-Au nanoparticles with Pd-to-Au molar ratios of 3:1 immobilized on multiwall carbon nanotubes (Pd3Au1/CNT) display high catalytic activity in the oxidant-free and acceptorless dehydrogenation and hydrogenation of N- and O-containing heterocyclic compounds, amines/imines, and alcohols/ketones. Transmission electron microscopy analysis demonstrates the preferential exposure of Pd3Au1(111) facets on the Pd3Au1/CNT catalyst. Mechanistic insights combining experimental data with density functional theory calculations reveal that the Pd3Au1(111) surface enhances both dehydrogenation and hydrogenation reactions and provides a rationale for the observed enhancements.

Développement de réacteurs microstructurés pour la conversion du propane en produits valorisés

Olivier Wolfrath

Industry requires continuously new chemical processes to convert raw materials to valuable products limiting the formation of by-products. Since a few years, an increasing interest has been given to the intensification of chemical processes. This represents a new approach in chemical reaction engineering and calls for a new type of chemical reactors: the microstructured reactors. They are characterized by miniature structures whose components have a sub-millimeter size. The flow channels, for example, have a diameter from ten to several hundred microns. The distinctive feature of these structures is a very large surface/volume ratio, namely between 10'000 and 50'000 m2/m3. In these conditions, heat transfer coefficient is very high, up to 25 kW · m-2 · K-1. It is accepted that the residence time distribution in a reactor strongly influences the product selectivity and yield. In these thin channels, the RTD is particularly narrow due to a short radial diffusion time (ms), allowing a precise control of the residence time. Another advantage of these microstructures is an increase of the inherent safety due to a small amount of the compounds used. However, fabrication of microreactors, especially the introduction of active catalyst in microchannels remains a difficult operation. And integration of microsystems in conventional chemical processes is still a challenge. The aim of this work is first to develop a novel membrane reactor based on a new microstructured catalytic packing in the filamentous form and to apply it to the nonoxydative dehydrogenation of propane. A second objective is to develop a reactor with micro heat exchangers allowing an optimized control of homogeneous reactions. This reactor was tested with the partial oxidation of propene to propylene oxide. The microstructured catalyst above is made of thin and long catalytic filaments placed in parallel with a tubular reactor. This new kind of catalyst is based on silica fibres covered by a γ-alumina layer. The position in parallel of these filaments of 7 μm diameter forces the gases to flow in the fibres direction between the filaments. The hydraulic diameter is about 70 μm. Due to this laminar and regular flow, the pressure drop in the bed was divided by 5 compared to a conventional bed (100-160 μm spheres) and the residence time distribution was particularly narrower. Such novel packing brings new opportunities to the heterogeneous catalysis domain because it can be used for many other reactions improving highly the hydrodynamics and keeping an excellent contact with the reactants. The microstructured catalyst was installed in two concentric zones of a tubular reactor separated by a palladium-silver membrane permeable to hydrogen. This product was removed from the gas phase to shift the thermodynamic equilibrium, enhancing the propane conversion from 22% up to 30%. Another significant advantage in this reactor is the increase of propene selectivity up to 97% in comparison to conventional industrial processes reaching 80-90%. This difference is due to the diminution of hydrogenolysis and hydroisomerization reactions. The dehydrogenation is known to be endothermic. Oxidation of the hydrogen passing through the membrane produced heat for this reaction along the catalytic zone. Moreover, a periodic regeneration by air allowed recovering the activity of the catalyst deactivated by coke formed during dehydrogenation. Periodic reaction operations allowed producing continuously propene with a high selectivity, and regenerating simultaneously the catalyst. The second microstructured reactor was developed integrating two micro heat exchangers at the inlet and outlet of a macroscopic tube. The aim is to heat up very fast the gas and to cool it down as well. Without these exchangers, heating and cooling duration corresponded each to about 20% of the total residence time. The use of the microstructures allowed diminishing significantly these durations (4-5% each). Applied to partial oxidation of propene, this reactor reached a more precise control of reaction temperature and duration. The propylene oxide (PO) selectivity was not increased with this system but, due to the microstructures, it was possible to work at higher temperatures where the reaction becomes very fast, without reaching an oxygen conversion of 100%. Indeed, it is essential to avoid this situation where oligomers and coke form dividing by 2 the PO selectivity. So another new kind of reactor was developed suitable for any fast exothermic reaction whose progression has to be limited because of potential consecutive reactions reducing, for example, the selectivity of an intermediate desired compound.

EPFL2001

Nanofibres de carbone sur filtre métallique comme support catalytique structuré

Pascal Tribolet

The main objectives of this work are 2-fold : The development of a novel type of composite material based on carbon nanofibers supported on sintered metal fibers filters (CNF/SMF) and to explore the use of this material as a catalytic support for a model reaction: selective hydrogenation of acetylene. The advantages of this novel support are: Due to carbon nanofibers, it combines a graphitic structure with a high specific surface area without microporosity. Supported carbon nanofibers can be used in a fixed bed reactor without very high pressure drop. Combination of two materials with high thermal conductivity gives a composite which keeps this property. It is suitable for highly exo/endothermic reactions, diminishing temperature gradients in the catalytic bed. The synthesis of carbon nanofibers on SMF filters was carried out by ethane catalytic decomposition at 655°C directly on metallic filters. An oxidation of SMF followed by a reduction in H2 create surface roughness, leading to a larger area for CNF nucleation. The CNF formation mechanism includes several steps: it starts with carbon deposition on metallic surface followed by its diffusion into the metal leading to carbides formation. When the limit of carbon solubility is attained, a layer of carbon is formed on the surface of metallic fibers. High tension within the bulk metal leads to carbide dissociation and by phase separation to graphite formation, which pushes the metallic particles through the carbon layer. Nickel, stainless steel an Inconel (an alloy of mainly nickel, iron and chromium) filters were used. The latter gave the highest uniformity of the carbon nanofibers layer showing an excellent mechanical stability. In order to control carbon deposition on the filters, a formal kinetic analysis of the decomposition reaction was undertaken. Partial orders of 1 for ethane, -2 for hydrogen and an apparent activation energy of 235 kJ/mol were obtained. The observed kinetics suggests strongly that the C – C bond scission is the rate determining step and not carbon diffusion into the metal which is often reported in the literature. The synthesis procedures like time on stream and reaction temperature were optimized: 1 hour of a mixture C2H6:H2:Ar (3:17:80) decomposition over SMFInconel at 655°C lead to ∼6% of carbon, leading to a CNF layer of 1 µm thickness covering the metallic fibers entirely. This material presents a high specific surface area (22.2 m2/g) and a low pressure drop for the gas flowing through. The carbon nanofibers have a diameter between 20 and 50 nm and a crystalline structure with platelets morphology where the graphene layers are stacked one above the other. Their surface is composed almost exclusively of carbon and hydrogen. Amongst the multiple possible applications of this novel composite material, its use as a catalyst support was assessed. Selective hydrogenation of acetylene was carried out over palladium supported on CNF/SMF and compared with commercial supports (ACF, EGF and AGF). The activated carbon fibers cloth (ACF) led to a Pd activity at least twice as E-type glass fibers tissue (EGF) or EGF covered by an alumina layer (AGF). Reaction kinetics was studied for Pd/ACF, leading to acetylene and hydrogen partial orders of -0.5 and 2.4, respectively and apparent activation energy of 50 kJ/mol. The negative partial order for C2H2 suggests high adsorption strength of this compound compared to other reagents on palladium. This particularity allows Pd to be selective. Hydrogenations are known to be structure sensitive. Therefore the catalyst activity for the model reaction depends on Pd particle size. It increases for large particle sizes. The control of this parameter was a priority. Variations of the palladium precursor, of the support and catalyst treatment were carried out. Micro-wave plasma was used since it is fast and has low energy consumption allowing chemically modifying the carbon support surface and activating catalyst after impregnation. This controls not only palladium sintering, but also decomposes tetraaminopalladate more efficiently, resulting in a catalyst activity of one order of magnitude higher. In order to control the palladium deposition on CNF/SMFInconel composite, it is important to have surface functional groups. The activation of carbon nanofibers was carried out with a 4 hours treatment in a boiling aqueous solution of hydrogen peroxide. This led to an amount on surface oxygen containing groups, per mass of carbon, higher than in ACF. Palladium particle size on the composite was controlled by support activation, the use of several metal precursors or different loadings or by a thermal treatment in argon at 500°C. Optimisation of the procedure allowed to obtain in a controlled way an average palladium particle sizes between 3.6 and 25 nm. The activity and selectivity towards ethylene of Pd/CNF/SMFInconel were observed to be higher compared to palladium supported on activated carbon, alumina or barite. Graphitic nature of carbon nanofibers, leading to strong metal-support interaction, was accounted as responsible for these improvements. The high thermal conductivity of the composite CNF/SMF ensured good heat transfer released due to the exothermicity of the reaction and allowed to work close to isothermal conditions in the catalytic bed. Finally it can be concluded, that for the first time carbon nanofibers synthesis was carried out in one step on sintered metal fibers filters, resulting in a novel structured composite material combining different specific properties and having promising potential applications.

EPFL2006

Rational Catalyst Design for Selective Hydrogenations

Daniel André Samuel Lamey

Catalyst design for selective hydrogenations is of major importance for the manufacturing of fine chemicals. Catalytic procedure which uses scarce and expensive noble metals is very challenging in terms of exclusive attack of a single functionality or substituent. The approach taken in this thesis is based on rational catalyst design that calls on a combination of catalyst synthesis and characterization. This has been applied for the design of catalysts suitable for industrially relevant reactions, i.e. the partial catalytic reduction of substituted nitroaromatic compounds and alkynes. Molybdenum nitrides were selected as they represent a more sustainable alternative to noble metals, less expensive and easy to prepare. First, beta-Mo2N was used to catalyze the liquid phase selective hydrogenation of a series of para-substituted nitroarenes to give the corresponding aromatic amine. Incorporation of low amounts (0.25% wt.) of Au nanoparticles on beta-Mo2N enhanced hydrogen uptake and catalytic activity while delivering an ultraselective response. In a second step, the influence on the catalytic response of nitride crystallographic phase (beta- vs. gamma-Mo2N) and surface area (7-66 m2 g-1) was examined. Both phases promoted the exclusive hydrogenation of p-chloronitrobenzene to p-chloroaniline where the beta-form delivered a higher specific (per m2) rate; the one for gamma-Mo2N was independent of surface area. The inclusion of Au on both nitrides served to enhance p-chloroaniline production. Finally, it was shown that incorporation of N in Mo structure can increase nitrobenzene hydrogenation rates on Mo2N samples with higher nitrogen content. In contrast, -C=O hydrogenolysis was favored with benzaldehyde as a result of lower N content. As a powerful tool for tailoring metal nanoparticle morphology, colloidal methods were used to design structured catalysts effective for the selective alkyne and âNO2 group reduction. The development of a catalyst based on polyvinylpyridine modified structured carbon nanofibers on sintered metal fibers supported (4 nm) polyvinylpyrrolidone (PVP) stabilized Pd was shown to be an optimum formulation for acetylene semi-hydrogenation where the catalyst shows high selectivity (93%) and stability with time-on-stream. We have established that reducing agent does not play a critical role in catalytic response while steric (vs. electronic) stabilizers and larger colloidal metal crystallites are more efficient. PVP-stabilized Ni nanocrystals were also prepared via colloidal method and tested in the m-dinitrobenzene hydrogenation were an antipathetic structure sensitivity was recorded. TOF and selectivity to m-nitroaniline exhibited a marked dependency on the presence of the stabilizer. It was attributed to preferential adsorption of PVP on selective edge and vertex atoms, leaving the plane atoms free. Supporting the Ni nanoparticles on activated carbon fibers and removing traces of PVP by a UV-ozone treatment resulted in a dramatic increase in selectivity to target m-NAN even at high conversions. Two-sites Langmuir-Hinshelwood kinetic model has been applied to rationalize the results. In summary, this thesis demonstrates that the product distribution can be controlled on a nano-level by tuning the properties of the active phase through modifications of the structural parameters (allotropic form, composition), modifications on the nanoparticle microenvironment (organic ligand shell) and optimization of particle size.

EPFL2015