Recent Advances in the Development of Highly Conductive Structured Supports for the Intensification of Non-adiabatic Gas-Solid Catalytic Processes: The Methane Steam Reforming Case Study

Structured catalysts are strong candidates for the intensification of non-adiabatic gas-solid catalytic processes thanks to their superior heat and mass transfer properties combined with low pressure drops. In the past two decades, different types of substrates have been proposed, including honeycomb monoliths, open-cell foams and, more recently, periodic open cellular structures produced by additive manufacturing methods. Among others, thermally conductive metallic cellular substrates have been extensively tested in heat-transfer limited exo- or endo-thermic processes in tubular reactors, demonstrating significant potential for process intensification. The catalytic activation of these geometries is critical: on one hand, these structures can be washcoated with a thin layer of catalytic active phase, but the resulting catalyst inventory is limited. More recently, an alternative approach has been proposed, which relies on packing the cavities of the metallic matrix with catalyst pellets. In this paper, an up-to-date overview of the aforementioned topics will be provided. After a brief introduction concerning the concept of structured catalysts based on highly conductive supports, specific attention will be devoted to the most recent advances in their manufacturing and in their catalytic activation. Finally, the application to the methane steam reforming process will be presented as a relevant case study of process intensification. The results from a comparison of three different reactor layouts (i.e. conventional packed bed, washcoated copper foams and packed copper foams) will highlight the benefits for the overall reformer performance resulting from the adoption of highly conductive structured internals.

Selective Catalytic Reduction of NOx Over Hierarchical Cu-ZSM-5 Coated on Ceramic Foam Support

The development of structured catalysts for process intensification is of growing interest in catalytic processes due to heat and mass transfer limitations at an industrial scale. This limitation can be...

Techniques of Preparation of Thin Films: Catalytic Combustion

Over the past several decades, an increasing amount of attention has been given to catalytic combustion as an environmentally friendly process. However, major impediments to large-scale application still arise on the materials side. Here, we review catalytic combustion on thin film catalysts in view of highlighting some interesting features. Catalytic films open the way for new designs of structured catalysts and the construction of catalysts for catalytic combustion. A special place is occupied by materials in the form of very thin films that reveal catalytic activity for various chemical reactions. In this review, we demonstrate the high catalytic activity of thin film catalysts in these oxidation reactions.

Study of Ni(0)/La2O3 perovskite coated on monolith substrates as a promising catalyst for CO2 dry reforming with steam reforming of methane in syn-gas production

Coated monolith/foam catalysts are promising materials for chemistry applications due to structured reactor configuratiions providing low expansion coefficient, good thermal stability and low pressure loss. In this study, powedered Ni(0)/La2O3 catalysts in perovskite structures, were deposited on cordierite monolith substrates (2MgO-2Al2O3-5SiO2) by dip-coating method. The catalysts were characterized by N2 adsorption, XRD, TPR-H2 analysis. The activity of structured catalysts with various powder loadings (4, 8, 12, 20 and 30 wt %) were evaluated in combined Steam-CO2 reforming reaction (CH4/CO2/H2O = 2/1/2 vol%) at GHSV = 60.000 h-1. XRD and TPR results showed that the active phase LaNiO3 were mainly Ni and La2O3distributed on the surface of cordierite channels after air calcination of 850oC, 3 hours and hydrogen reduction of 600oC, 2 hours . The conversion of methane and CO2 on monolith catalysts, with proper active sites loadings of 12 – 20 wt%, were close to 80 vol% at 800oC. At the same reaction amount of active sites, the feedstock conversion on LaNiO3/monolith (12 %wt LaNiO3/monolith) was significantly higher than on corresponding powdered type, respectively 1.6 times of CH4, 1.8 times of CO2 conversion.

Cu/ZSM5-Geopolymer 3D-Printed Monoliths for the NH3-SCR of NOx

Geopolymer-based monoliths manufactured by direct ink writing, containing up to 60% by weight of presynthesized ZSM5 with low Si/Al ratio, were investigated as structured catalysts for the NH3-SCR of NOx. Copper was introduced as the active metal by ion exchange after a preliminary acid treatment of the monoliths. Monolithic catalysts were characterized by morphological (XRD and SEM), textural (BET and pore size distribution), mechanical (compressive strength), chemical (ICP–MS), redox (H2-TPR) and surface (NH3-TPD) analyses, showing the preservation of Cu-exchanged zeolite features in the composite monoliths. NH3-SCR tests, carried out on both monolithic and powdered samples in the temperature range 70–550 °C, confirmed that composite monoliths provide a very good activity and a high selectivity to N2 over the whole range of temperatures explored due to the hierarchical structure of the materials, in addition to a good mechanical resistance—mostly related to the geopolymer matrix.

Modern Trends in Design of Catalysts for Transformation of Biofuels into Syngas and Hydrogen: From Fundamental Bases to Performance in Real Feeds

This review considers problems related to design of efficient structured catalysts for natural gas and biofuels transformation into syngas. Their active components are comprised of fluorite, perovskite and spinel oxides or their nanocomposites (both bulk and supported on high surface area Mg-doped alumina or MgAl2O4) promoted by platinum group metals, nickel and their alloys. A complex of modern structural, spectroscopic and kinetic methods was applied to elucidate atomic-scale factors controlling their performance and stability to coking, such as dispersion of metals/alloys, strong metal-support interaction and oxygen mobility/reactivity as dependent upon their composition and synthesis procedures. Monolithic catalysts comprised of optimized active components loaded on structured substrates with a high thermal conductivity demonstrated high activity and stability to coking in processes of natural gas and biofuels reforming into syngas. A pilot-scale axial reactor equipped with the internal heat exchanger and such catalysts allowed to efficiently convert into syngas the mixture of natural gas, air and liquid biofuels in the autothermal reforming mode at low (~50–100 °C) inlet temperatures and GHSV up to 40,000 h−1.