Catalytic Properties of Ag/Al2O3 Catalysts for Lean NOx Reduction Processes and Characterisation of Active Silver Species

A study of the lean NO _x reduction activity employing different reductants over Ag/Al₂O₃ samples prepared from reverse microemulsions or impregnation with EDTA-complexes is presented. A multitechnique approach is employed for characterisation of the samples and/or processes taking place in the course of the NO _x -SCR reaction with propene and propane. Results by in situ-DRIFTS reveal that, for the propene reductant, silver provides a new path for hydrocarbon activation involving generation of adsorbed acrylate species as a partially oxidised active intermediate, in line with previous proposals for other non-noble metal systems. It is shown, mainly on the basis of XAFS studies, that active silver species are related to well dispersed silver aluminate-like phases with tetrahedral local symmetry and a relatively high disorder in the oxygen first shell.     

Selective catalytic reduction of NOx using propene and ethanol over catalysts of Ag/Al2O3 prepared by microemulsion and promotional effect of hydrogen

The present study explores the possibilities of catalysts of Ag/Al₂O₃, in which silver has been deposited using reverse microemulsions with the aim of getting maximum dispersion and homogeneity in the active superficial species, for the selective catalytic reduction of NO_x in excess of oxygen, using both propene and ethanol as reductants and in the scope of the control of the emissions produced by vehicles that operate in conditions of lean mixture like the diesel engine or those of gasoline direct injection. The promotional effect of the hydrogen presence in the reactive mixture has also been analyzed. For both reductants, when in presence of hydrogen, an important enhancement in NO_x conversion is produced, in particular for a catalyst with 3 wt.% silver. The production of acetaldehyde during the reaction employing ethanol is also analyzed and its role on the NO_x reduction process has been examined. The interpretation of catalytic properties has been complemented by means of in-situ DRIFTS.     

Reduction of NOx Stored at Low Temperatures on a NOx Adsorbing Catalyst

Isothermal storage and reduction of NO₂ with CO, C₃H₆ and H₂ as reducing agents on a lean NO _x adsorber was investigated by temperature programmed desorption (TPD) and temperature programmed reduction (TPR) studies. The reduction of NO _x was clearly favoured with H₂ as reducing agent. Carbon monoxide and C₃H₆ showed fairly low reduction of NO _x . The NO _x reduction at low temperatures with H₂ as reducing agent was found to be effective, clearly much more effective than for CO.     

Non-thermal plasma-assisted catalytic NOx storage over Pt/Ba/Al2O3 at low temperatures

NO_x storage performances have been investigated on a Pt/Ba/Al₂O₃ catalyst by comparison using two types of non-thermal plasma (NTP) reactor: the “PDC system” reactor and the “PFC system” reactor. In the PDC system, the catalyst was placed in the discharge space and was activated by the plasma directly, whereas in the PFC system, the plasma reactor was followed by the catalyst. The results showed that the NO_x storage capacity (NSC) of the Pt/Ba/Al₂O₃ catalyst was significantly enhanced by the non-thermal plasma in the PDC and PFC system, and the PDC system exhibited better promotional effect than the PFC system in the temperature range of 100–300 °C. The NSC of the catalyst was increased with the increase of the input energy density both in the PDC and PFC system due to the higher NO oxidation at higher input energy density. It was also found that the ionic wind induced by plasma in the PDC system enhanced the quantity of the NO adsorbed onto the catalyst surface and therefore could react with the O-radical to form more NO₂, and thus promote the formation of nitrate on the catalyst.     

Support modification to improve the sulphur tolerance of Ag/Al2O3 for SCR of NOx with propene under lean-burn conditions

Ag/Al₂O₃ catalysts with 1 wt% SiO₂ or TiO₂ doping in alumina support have been prepared by wet impregnation method and tested for sulphur tolerance during the selective catalytic reduction (SCR) of NO_x using propene under lean conditions. Ag/Al₂O₃ showed 44% NO_x conversion at 623 K, which was drastically reduced to 21% when exposed to 20 ppm SO₂. When Al₂O₃ support in Ag/Al₂O₃ was doped with 1 wt% SiO₂ or TiO₂ the NO_x conversion remained constant in presence of SO₂ showing the improved sulphur tolerance of these catalysts. Subsequent water addition does not induce significant deactivation. On the contrary, a slight promotional effect on the activity of NO conversion to nitrogen is observed after Si and Ti incorporation. FTIR study showed the sulphation of silver and aluminum sites of Ag/Al₂O₃ catalysts resulting in the decrease in the formation of reactive intermediate species such as –NCO, which in turn decreases NO_x conversion to N₂. In the case of Ag/Al₂O₃ doped with SiO₂ or TiO₂, formation of silver sulphate and aluminum sulphate was drastically reduced, which was evident in FTIR resulting in remarkable improvement in the sulphur tolerance of Ag/Al₂O₃ catalyst. These catalysts before and after the reaction have been characterized with various techniques (XRD, BET surface area, transmittance FTIR and pyridine adsorption) for physico-chemical properties.     

Steady State Isotopic Transient Kinetic Analysis of Flameless Methane Combustion over Pd/Al2O3 and Pt/Al2O3 Catalysts

The SSITKA measurements were performed in the steady state of complete methane oxidation on the Pd/Al₂O₃ and Pt/Al₂O₃ catalysts. It was found that the number of intermediates and their average life-time on the catalyst surface changes with the increase of reaction temperature. On the Pd/Al₂O₃ catalyst there is larger number of active centres than on Pt/Al₂O₃ catalyst which permits the course of methane oxidation at lower temperatures.     

Influence of the Storage Material on the Storage of NOx at Low Temperatures

The NO _x storage performance at low temperature (100–200 °C) has been studied for model NO _x storage catalysts. The catalysts were prepared by sequentially depositing support, metal oxide and platinum on ceramic monoliths. The support material consisted of acidic aluminium silicate, alumina or basic aluminium magnesium oxide, and the added metal oxide was either ceria or barium oxide. The NO _x conversion was evaluated under net-oxidising conditions with transients between lean and rich gas composition and the NO _x storage performance was studied by isothermal adsorption of NO₂ followed by temperature programmed desorption of adsorbed species. The maximum in NO _x storage capacity was observed at 100 °C for all samples studied. The Pt/BaO/Al₂O₃ catalyst stored about twice the amount of NO _x compared with the Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ samples. The storage capacity increased with increasing basicity of the support material, i.e. Pt/Al₂O₃·SiO₂ < Pt/Al₂O₃ < Pt/Al₂O₃ · MgO. Water did not significantly affect the NO _x storage performance for Pt/Al₂O₃ or Pt/BaO/Al₂O₃.     

The Effect of a Changing Lean Gas Composition on the Ability of NO2 Formation and NOx Reduction over Supported Pt Catalysts

Three model catalysts (Pt/Al₂O₃, Pt/TiO₂, Pt/V₂O₅/TiO₂) were examined in regard to their NO₂ formation ability under a changing lean gas composition. The results show that the NO to NO₂ oxidation function as well as the NO _x reduction under lean gas conditions is affected by a change in the lean gas atmosphere. The NO oxidation activity also decreased with time, for Pt/Al₂O₃ and Pt/TiO₂, and a possible explanation may be platinum oxide formation. This deactivation was not observed for Pt/V₂O₅/TiO₂.     

Effect of Co and Rh promoter on NOx storage and reduction over Pt/BaO/Al2O3 catalyst

Effect of cobalt and rhodium promoter on NO_x storage and reduction (NSR) kinetics was investigated over Pt/BaO/Al₂O₃. Kinetics of 2% cobalt loading over Pt/BaO/Al₂O₃ demonstrated highest NO_x uptake during lean cycle, while reduction efficiency during rich cycle appeared most poor. In contrast to this, rhodium showed suppressing effect of NO_x uptake during lean cycle and demonstrated an enhanced effect for the higher efficiency of NO_x reduction during rich cycle. DRIFT study for NO_x uptake and regeneration confirmed formation of surface BaNO_x from the band at 1300 cm⁻¹ and formation of bulk BaNO_x from the band at 1330 cm⁻¹.     

NOx Reduction over CeO2–ZrO2 Supported Iridium Catalyst in the Presence of Propanol

The 1-propanol assisted-reduction of NO _x was investigated over Ir/Ce_0.6Zr_0.4O₂. The catalytic performances of such a catalyst, the associated FTIR characterizations, and transient experiments suggest the formation of adsorbed R-NO _x species as intermediates of the deNO _x process; they provide the partially oxidized species required by the deNO _x model.     

Reduction of NO by CO on Cu/ZrO2/Al2O3 catalysts: Characterization and catalytic activities

ZrO₂, γ-Al₂O₃ and ZrO₂/γ-Al₂O₃-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H₂, Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO₂/γ-Al₂O₃ matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO₂. Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO₂.     

Phase diagram of the Al2O3-HfO2-Y2O3 system

The phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al₂O₃ + HfO₂ + Y₃Al₅O₁₂. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system.     

Supported Heteropolyacids for NOx Storage and Reduction

TiO₂ and SnO₂ were studied as possible supports for HPW in order to produce a new type of sorbent for NO _x trap applications. SnO₂ was synthesised by various inorganic methods while TiO₂ was purchased commercially. The sorption capacities and efficiencies depend upon the BET surfaces. Best performances were obtained with support with large pores where the crystalline structure of HPW is maintained. The optimal loading of HPW is ca. 50% with BET surface in the range 20–80 m²g^–1.     

Corrosion mechanisms of Al2O3/MgAl2O4 by V2O5, NiO, Fe2O3 and vanadium slag

The effects of V₂O₅, NiO, Fe₂O₃ and vanadium slag on the corrosion of Al₂O₃ and MgAl₂O₄ have been investigated. The specimens of Al₂O₃ and MgAl₂O₄ with the respective oxides above mentioned were heated at 10 °C/min from room temperature up to three different temperatures: 1400, 1450 and 1500 °C. The corrosion mechanisms of each system were followed by XRD and SEM analyses. The results obtained showed that Al₂O₃ was less affected by the studied oxides than MgAl₂O₄. Alumina was only attacked by NiO forming NiAl₂O₄ spinel, while the MgAl₂O₄ spinel was attacked by V₂O₅ forming MgV₂O₆. It was also observed that Fe₂O₃ and Mg, Ni, V and Fe present in the vanadium slag diffused into Al₂O₃. On the other hand, the Fe₂O₃ and Ca, S, Si, Na, Mg, V and Fe diffused into the MgAl₂O₄ structure. Finally, the results obtained were compared with those predicted by the FactSage software.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Laser machining of Al2O3-ZrO2 (3%Y2O3) eutectic composite

In this work we present the study of the interaction between NIR pulsed laser and Al₂O₃-ZrO₂ (3%Y₂O₃) eutectic composite. The effect produced by modifying the reference position as well as the working conditions and laser beam features has been studied when the samples are processed by means of pulse bursts.The samples were obtained by the laser floating zone technique using a CO₂ laser system. The laser machining was carried out with a Q-switched Nd:YAG laser at its fundamental wavelength of 1064 nm with pulse-widths in the nanosecond range.Geometric dimensions, i.e. ablated depth, machined width and removed volume as well as ablation yield of the resulting holes have been studied. We have described and discussed the morphology, composition and microstructure of the processed samples.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Influence of low concentration of SO2 for selective reduction of NO by C3H8 in lean-exhaust conditions on the activity of Ag/Al2O3 catalyst

The effect of SO₂ for the selective reduction of NO by C₃H₈ on Ag/Al₂O₃ was investigated in the presence of excess oxygen and water vapor. The NO_x conversion decreased permanently even in the presence of a low concentration of SO₂ (0.5–10 ppm) at <773 K. The increase in SO₂ concentration resulted in a large decrease in NO_x conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al₂O₃ remained constant even in the presence of 10 ppm of SO₂. The sulfate species formed on the used Ag/Al₂O₃ were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNO_x activity on the Ag/Al₂O₃. The sulfated Ag/Al₂O₃ was appreciably regenerated by thermal treatment in the deNO_x feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO₂ for long time by the heat treatment at every 20 h intervals.