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.     

Experimental and theoretical study of gas/solid mass transfer in metallic filters as supports for micro-structured catalysts

Commercial sintered metallic micro-fibers have been investigated in view of their adoption as enhanced catalyst carriers. The material herein studied has high porosity (86%) and very high interfacial area (22 400 m²/m³), thus appearing promising for application in fast, mass-transfer limited catalytic processes. It was catalytically activated by calcination and impregnation with Pt, and tested in the model reaction of CO oxidation. The observed activity was very high: at T>500 °C, under diffusional control, CO conversions in excess of 90% were achieved at space velocities in the order of 10⁶ h^?1. Dimensionless mass transfer coefficients extracted from these data, accounting also for axial dispersion, exhibited. However, negative deviations from those expected either for a single infinite cylinder or from extrapolation of previous correlations for open-celled foams at higher Reynolds numbers. According to an original and unifying theoretical approach herein proposed, such deviations are quantitatively explained by accounting for the limitations to boundary layer development due to the proximity of other fibers in the densely packed system. The key point is to assume a pseudo ordered locally parallel assembly of cylinders with average distance related to the fiber diameter and to the void fraction.     

Absolute measurement of planarity with Fritz's method: uncertainty evaluation

Fritz's method [Opt. Eng. 23, 379 (1984)] of using Zernike polynomials to assess the absolute planarity of test plates is revisited. A refinement is described that takes into account the data decorrelation that appears in experiments. An uncertainty balance is defined by propagation of error contributions through the steps of the method. The resultant measuring procedure is demonstrated on a data set from experiments, and a nanometer level of uncertainty is achieved.     

Role of Nitrate Species in the “NO2-SCR” Mechanism over a Commercial Fe-zeolite Catalyst for SCR Mobile Applications

The NO₂-SCR reaction is studied by transient reaction analysis over a Fe-zeolite commercial catalyst. It is proposed that the NO₂-SCR reaction occurs according to a mechanism wherein surface nitrates are first formed by NO₂ disproportionation, followed by their catalytic reduction to nitrogen by ammonia.     

Higher Alcohol Synthesis

It has been known for many years that it is possible to produce mixtures of methanol and higher alcohols from synthesis gas by alkali promotion of the methanol synthesis catalysts and by appropriate modification of the reaction conditions [l]. From 1927 to 1945 plants were in operation in the United States and Germany, that were dismantled with the coming of different feedstocks and the necessity of obtaining pure alcohols for chemical use. In the last decade the chemical and petroleum industry has shown a renewed and growing interest in the use of mixtures of methanol and higher aliphatic alcohols. The original goal in the late '70s was mainly to reduce oil dependence by producing synthetic components for gasoline blends. More recently the trend to lead phase-down due to environmental protection has focused the attention on the product performances of such alcohol mixtures as high octane blending stock for gasoline. It has been shown that the addition of higher alcohols to methanol increases the water tolerance in respect to phase separation, reduces the fuel volatility and the vapor lock tendency, and also results in higher volumetric heating values.     

An experimental investigation of Fischer–Tropsch synthesis over washcoated metallic structured supports

In principle, the application of monolithic catalysts to the Fischer–Tropsch synthesis can solve many of the problems related to the classical Fischer–Tropsch reactors, in particular concerning the necessity to operate with short diffusion distances and low pressure drops, preferably according to the ideal plug-flow behavior, while still maintaining a reasonable inventory of catalytic material in the reactor volume.The preparation of prototype cobalt-based catalysts, washcoated onto metallic structured supports with different geometries, is described herein, together with the evaluation of the catalytic properties of such systems in the Fischer–Tropsch synthesis at industrially relevant process conditions (220–235 °C, 20 bar, 2.1  mol_H2/mol_CO,  5000 cm³(STP)_CO+H2/h/g_cat). Comparative tests with the same catalyst in the powdered form were also carried out at the same process conditions.It was found that the structured catalysts maintained the activity and the selectivity of the original powdered catalyst, provided that the washcoat thickness is sufficiently thin.     

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.     

Transient kinetic study of the SCR-DeNOx reaction

The unsteady-state kinetics of the selective catalytic reduction (SCR) of NO with NH₃ is studied over V₂O₅–WO₃/TiO₂ model catalysts by means of the transient response method. NH₃ strongly adsorbs onto the catalyst surface whereas NO does not adsorb appreciably. A dynamic mathematical model based on a Temkin-type desorption process for NH₃ and a SCR reaction rate with a complex dependence on the ammonia surface coverage is well suited to represent the data.