Honeycomb supports with high thermal conductivity for gas/solid chemical processes

The scope of this review article is to address the use of novel monolithic catalysts with high thermal conductivity in externally cooled tubular reactors for gas/solid exothermic chemical processes in place of conventional packed beds of catalyst pellets.

After discussing the analysis and the implications of heat conduction in honeycomb monolith structures, we review herein simulation studies and experimental investigations showing that near-isothermal reactor operation can be achieved even under very high thermal loads by adopting specific materials and designs of the honeycomb supports associated with high effective radial thermal conductivities. For such monoliths, the limiting thermal resistance is located at the interface between the monolith and the inner tube wall (“gap resistance”). Recent measurements of the “gap” heat transfer coefficient point to very large values (>400 W/(m² K)), which are controlled both by the tube–monolith clearance at the actual operating conditions and by the thermal conductivity of the process gas.     

How to control the selectivity in the reduction of NOx with H2 over Pt-Ba/Al2O3 Lean NOx Trap catalysts

The reduction process of NO_x species stored over Pt-Ba/Al₂O₃ Lean NO_x Trap systems is analysed in this paper when H₂ is used as a reductant. The effect of different experimental conditions (temperature, reductant concentration, adsorption lengths, etc.) is addressed and discussed in relation to the selectivity and the efficiency of the reduction process.     

NH3-NO/NO2 SCR for diesel exhausts after treatment: mechanism and modelling of a catalytic converter

We review herein the key mechanistic and kinetic features of the reactions involved in the NH₃-NO/NO₂ SCR system investigated by dynamic reactive experiments over a V-based commercial powdered catalyst, eventually leading to the proposal of an original redox scheme which accounts for stoichiometry, selectivity and intrinsic kinetics of the global SCR process.     

NH3–NO/NO2 SCR for Diesel Exhausts Aftertreatment: Reactivity, Mechanism and Kinetic Modelling of Commercial Fe- and Cu-Promoted Zeolite Catalysts

The activity and the mechanism of the main reactions in the NO/NO₂–NH₃ SCR reacting system were comparatively investigated over a Fe- and a Cu-promoted commercial zeolite catalyst for the aftertreatment of Diesel exhausts. A dynamic micro-kinetic model in close agreement with all the details of the SCR catalytic chemistry was also developed.     

Catalytic combustion of gasified biomasses over Mn-substituted hexaaluminates for gas turbine applications

The catalytic combustion of gasified biomasses over Mn-substituted hexaaluminates with high thermal stability is addressed. Combustion activity tests of the main fuel components, i.e. CO, H₂, C₂H₄ and CH₄, have been performed, and the effects of H₂O and CO₂ on the fuel combustion have been investigated. The reactivity of NH₃ in the catalytic combustion has also been studied in view of its potential source of undesired fuel-NO_x. Lab-scale data have been preliminarily scaled up through mathematical modeling.     

Addition of propene to carbon monoxide-hydrogen in higher alcohol synthesis over unpromoted and caesium-promoted ZnCrO catalysts

Catalytic activity tests in higher alcohol synthesis over unpromoted and caesium-promoted ZnCrO catalysts with the addition of propene to CO-H₂ have been performed to clarify the role of alkenes in the chain growth to higher oxygenates. Over the unpromoted catalyst, the observed increments of selected products (1-butanol, 2-methyl-1-butanol, 1-methoxy-2-methyl-butane, C₇ ketone) upon the addition of propene are consistent with the occurrence of a hydrocarbonylation reaction of propylene to an aldehydic linear C₄ intermediate, which is successively transformed according to previously established reaction paths of higher alcohol synthesis over ZnCrO catalysts. Hydrocarbonylation is slower than aldol condensation, and the influence of propene addition is greatly reduced over the caesium-promoted catalyst as well as at higher reaction temperatures. We conclude that the contribution of alkenes to the reaction scheme of higher alcohol synthesis over alkali-promoted ZnCrO catalysts is apparently unimportant.     

A C1 microkinetic model for methane conversion to syngas on Rh/Al2O3

A microkinetic model capable of describing multiple processes related to the conversion of natural gas to syngas and hydrogen on Rh is derived. The parameters of microkinetic models are subject to (intrinsic) uncertainty arising from estimation. It is shown that intrinsic uncertainty could markedly affect even qualitative model predictions (e.g., the rate‐determining step). In order to render kinetic models predictive, we propose a hierarchical, data‐driven methodology, where microkinetic model analysis is combined with a comprehensive, kinetically relevant set of nearly isothermal experimental data. The new, thermodynamically consistent model is capable of predicting several processes, including methane steam and dry reforming, catalytic partial oxidation, H₂ and CO rich combustion, water‐gas shift and its reverse at different temperatures, space velocities, compositions and reactant dilutions, using the measured Rh dispersion as an input. Comparison with other microkinetic models is undertaken. Finally, an uncertainty analysis assesses the effect of intrinsic uncertainty and catalyst heterogeneity on the overall model predictions. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Dominant Reaction Pathways in the Catalytic Partial Oxidation of CH4 on Rh

Reforming technologies are at the heart of converting fossil fuels and biofuels to syngas and hydrogen for novel energy applications and, among reforming technologies, catalytic partial oxidation is appealing for decentralized energy production due to the compactness of reactors. Yet, the mechanisms of these reactions are poorly understood. Here we combine fundamental surface chemistry and detailed reactor models to elucidate the pathways leading to syngas and propose strategies for optimizing the process.     

Experimental and modeling analysis of the effect of catalyst aging on the performance of a short contact time adiabatic CH4-CPO reactor

Catalytic partial oxidation of methane at short contact time was studied in a lab-scale packed bed reactor over a 0.5 wt% Rh/A₂O₃ catalyst. Experiments were focused on the investigation of catalyst stability and durability upon repeated start-up/shut-down tests at different inlet temperatures and flow rates. Measurements of the axial temperature profiles evidenced a high sensitivity of the steady state thermal behavior of the reactor on catalyst activity: a decrease of the intrinsic catalytic activity was interpreted as the cause of a progressive over-heating of the bed which, in turn, moderated the loss of methane conversion and syngas productivity. At sufficiently high flow rate the observed temperature rise spread along the whole catalytic bed. Under such conditions both steady state and dynamic reactor performances were affected by the progressive decay of catalyst activity. A rationalization of the observed results was pursued by applying a one dimensional (1D) heterogeneous model of the reactor to the quantitative analysis of experimental results. Model predictions revealed the occurrence of operating surface temperatures up to 1100 °C and allowed to quantify the progressive worsening of reactor performances in terms of a loss of reforming activity localized in correspondence of the catalyst hot spot.