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.     

An investigation of the thermal stability and sulphur tolerance of Ag/γ-Al2O3 catalysts for the SCR of NOx with hydrocarbons and hydrogen

The sulphur tolerance and thermal stability of a 2 wt% Ag/γ-Al₂O₃ catalyst was investigated for the H₂-promoted SCR of NO_x with octane and toluene. The aged catalyst was characterised by XRD and EXAFS analysis. It was found that the effect of ageing was a function of the gas mix and temperature of ageing. At high temperatures (800 °C) the catalyst deactivated regardless of the reaction mix. EXAFS analysis showed that this was associated with the Ag particles on the surface of the catalyst becoming more ordered. At 600 and 700 °C, the deactivating effect of ageing was much less pronounced for the catalyst in the H₂-promoted octane-SCR reaction and ageing at 600 °C resulted in an enhancement in activity for the reaction in the absence of H₂. For the toluene + H₂-SCR reaction the catalyst deactivated at each ageing temperature. The effect of addition of low levels of sulphur (1 ppm SO₂) to the feed was very much dependent on the reaction temperature. There was little deactivation of the catalyst at low temperatures (≤235 °C), severe deactivation at intermediate temperatures (305 and 400 °C) and activation of the catalyst at high temperatures (>500 °C). The results can be explained by the activity of the catalyst for the oxidation of SO₂ to SO₃ and the relative stability of silver and aluminium sulphates. The catalyst could be almost fully regenerated by a combination of heating and the presence of hydrogen in the regeneration mix. The catalyst could not be regenerated in the absence of hydrogen.     

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.     

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.     

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.     

Exceptional Activity for NOx Reduction at Low Temperatures Using Combinations of Hydrogen and Higher Hydrocarbons on Ag/Al2O3 Catalysts

The effect of the addition of hydrogen on the SCR of NO _x with a hydrocarbon reaction was investigated. It was found that hydrogen had a remarkable effect on the temperature range over which NO _x could be reduced during the SCR reaction with octane. Reduction of NO _x was initiated at as low a temperature as 100 °C and >95% NO _x conversion was achieved over a temperature range of 200–450 °C. Hydrogen has the effect of activating octane at lower temperatures and also promotes the oxidation of NO to NO₂ in the absence of hydrocarbon. Transient kinetic and in situ DRIFTS measurements indicated that hydrogen has a direct role in the reaction mechanism by either promoting the formation and storage of an organic C = N species which can then readily reduce NO _x and/or removing a species which acts as a poison to the SCR reaction at low temperatures.     

Novel promoting effect of SO2 on the selective catalytic reduction of NOx by ammonia over Co3O4 catalyst

Spinel nano-Co₃O₄ was prepared by solid-state reaction at room temperature and investigated for selective catalytic reduction of NO_x by NH₃ (NH₃-SCR). Although suffering from pore filling and plugging, treatment of this catalyst by SO₂ showed novel promoting effect on NH₃-SCR above 250 °C. Bulk cobalt sulfate was observed over the sulfated Co₃O₄ with XRD, which would be an active component for NH₃-SCR. The sulphated Co₃O₄ catalyst exhibited good resistance to SO₂ (500 ppm, 100 ppm) and 10% H₂O at a space velocity of about 25 000 h⁻¹ at 300 °C, as tested for 12 h.     

Improvement of catalytic activity and sulfur-resistance of Ag/TiO2–Al2O3 for NO reduction with propene under lean burn conditions

Ag-based catalysts supported on various metal oxides, Al₂O₃, TiO₂, and TiO₂–Al₂O₃, were prepared by the sol–gel method. The effect of SO₂ on catalytic activity was investigated for NO reduction with propene under lean burn condition. The results showed the catalytic activities were greatly enhanced on Ag/TiO₂–Al₂O₃ in comparison to Ag/Al₂O₃ and Ag/TiO₂, especially in the low temperature region. Application of different characterization techniques revealed that the activity enhancement was correlated with the properties of the support material. Silver was highly dispersed over the amorphous system of TiO₂–Al₂O₃. NO₃⁻ rather than NO₂⁻ or NOx reacted with the carboxylate species to form CN or NCO. NO₂ was the predominant desorption species in the temperature programmed desorption (TPD) of NO on Ag/TiO₂–Al₂O₃. More amount of formate (HCOO⁻) and CN were generated on the Ag/TiO₂–Al₂O₃ catalyst than the Ag/Al₂O₃ catalyst, due to an increased number of Lewis acid sites. Sulfate species, resulted from SO₂ oxidation, played dual roles on catalytic activity. On aged samples, the slow decomposition of accumulated sulfate species on catalyst surface led to poor NO conversion due to the blockage of these species on active sites. On the other hand, catalytic activity was greatly enhanced in the low temperature region because of the enhanced intensity of Lewis acid site caused by the adsorbed sulfate species. The rate of sulfate accumulation on the Ag/TiO₂–Al₂O₃ system was relatively slow. As a consequence, the system showed superior capability for selective adsorption of NO and SO₂ toleration to the Ag/Al₂O₃ catalyst.     

Effect of SO2 on the catalytic activity of Ga2O3–Al2O3 for the selective reduction of NO with propene in the presence of oxygen

The effect of coexisting SO₂ on the catalytic activity of Ga₂O₃–Al₂O₃ prepared by impregnation, coprecipitation and sol–gel method for NO reduction by propene in the presence of oxygen was studied. Although the activity of Al₂O₃ and Ga₂O₃–Al₂O₃ prepared by impregnation (Ga₂O₃/Al₂O₃(I)) and coprecipitation (Ga₂O₃–Al₂O₃(CP)) was depressed considerably by the presence of SO₂, NO conversion on Ga₂O₃–Al₂O₃ prepared by sol–gel method (Ga₂O₃–Al₂O₃(S)) was not decreased but increased slightly by SO₂ at temperatures below 723 K. From catalyst characterization, SO₂ treatment was found to cause two important effects on the surface properties: one is the creation of Brønsted acid sites on which propene activation is promoted (positive effect), and the other is the poisoning of NO_x adsorption sites on which NO reduction proceeds (negative effect). It was presumed that the influence of SO₂ treatment on the catalytic activity is strongly related to the balance between the negative and positive. The activity enhancement of Ga₂O₃–Al₂O₃(S) by SO₂ was accounted for by the following consideration: (1) increase of the propene activation ability by SO₂, (2) incomplete inhibition of NO_x adsorption sites by SO₂.     

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.     

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.     

A comparison study on non-thermal plasma-assisted catalytic reduction of NO by C3H6 at low temperatures between Ag/USY and Ag/Al2O3 catalysts

A comparison study was carried out on non-thermal plasma (NTP)-assisted selective catalytic reduction (SCR) of NO_x by propene over Ag/USY and Ag/Al₂O₃ catalysts. Ag/USY was almost inactive in thermal SCR while it showed obvious activities in NTP-assisted SCR at 100 °C–200 °C. Although the NO_x conversion over Ag/Al₂O₃ was also enhanced at 300 °C–400 °C by the assistance of NTP, it was ineffective below 250 °C. The intermediates over Ag/USY and Ag/Al₂O₃ were investigated using in situ DRIFTS method. It was found that key intermediates in HC-SCR, such as NCO, CN, oxygenates and some N-containing organic species were enriched after the assistance of NTP. The differences in the behaviors of above intermediates were not found between these two kinds of catalysts. However, some evidences suggested that different properties of the absorbed NO_x species resulted in the distinction of SCR reactions over Ag/USY and Ag/Al₂O₃. TPD profiles of Ag/Al₂O₃ showed that nitrates formed over the catalyst were quite stable at low temperatures, which might occupy the active sites and were unfavorable to SCR reactions. The nitrates over Ag/USY were unstable, among which the unidentate nitrate species is probably contributed to the SCR reactions at low temperatures.     

Al2O3-coated SnO2/TiO2 composite electrode for the dye-sensitized solar cell

A novel Al₂O₃-coated SnO₂/TiO₂ composite electrode has been applied to the dye-sensitized solar cell. In such an electrode, two kinds of energy barriers (SnO₂/TiO₂ and TiO₂/Al₂O₃) were designed to suppress the recombination processes of the photo-generated electrons and holes. After the SnO₂ was modified by colloid TiO₂, the photoelectric conversion efficiency of the SnO₂/TiO₂ composite cell increased to 2.08% by a factor of 2.8 comparing with that of the SnO₂ cell. The Al₂O₃ layer on the SnO₂/TiO₂ composite electrode further suppressed the generation of the dark current, resulting in 37% improvement in device performance comparing with the SnO₂/TiO₂ cell.     

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.     

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.     

Matrix–filler interactions in polysilazane-derived ceramics with Al2O3 and ZrO2 fillers

Interactions between a poly(vinyl)silazane and Al₂O₃ or Y₂O₃-stabilised ZrO₂ fillers were studied during the fabrication of polysilazane-derived bulk ceramics in order to investigate the influence of oxide fillers on resulting properties. Specimens were produced by coating of the filler powders with the polysilazane, warm-pressing of the resulting composite powders, and pyrolytic conversion in flowing N₂ at various temperatures between 1000 °C and 1400 °C. Significant differences in densification were observed, depending on the filler used. Reactions between the polysilazane-derived matrix and Al₂O₃ or ZrO₂ at temperatures ≥1300 °C resulted in the formation of Si₅AlON₇ or ZrSiO₄, respectively. Reactivity in the polysilazane-derived component was a result of SiO₂ contamination caused primarily by adsorbed species on the filler particle surface. Knowledge of polysilazane/filler interface processes is found to be decisive for the prediction of properties such as shrinkage and porosity, which heavily influence performance of a material.     

Properties and rapid consolidation of nanostructured Al2O3-Al2SiO5 composites by high frequency induction heated sintering

The rapid sintering of nanostructured Al₂O₃ and Al₂O₃ to Al₂SiO₅ composites was investigated by a high-frequency induction heating sintering process. The advantage of this process is that it allows very quick densification to near theoretical density and inhibition of grain growth. Highly dense nanostructured Al₂O₃ and Al₂O₃ to Al₂SiO₅ composites were produced with simultaneous application of a 80 MPa pressure and induced output current of a total power capacity (15 kW) within 3 min. The sintering behavior, grain size and mechanical properties of Al₂O₃ and Al₂O₃ to Al₂SiO₅ composites were investigated.     

A novel solid superbase of Eu2O3/Al2O3 and its catalytic performance for the transesterification of soybean oil to biodiesel

A novel solid superbase catalyst of Eu₂O₃/Al₂O₃ was prepared and its basic strength reached 26.5 measured by indicators according to Hammett scale. The catalytic activity of Eu₂O₃/Al₂O₃ was evaluated for the transesterification of soybean oil with methanol to biodiesel in the fixed bed reactor and under atmospheric pressure. The results show that Eu₂O₃/Al₂O₃ is an excellent catalyst for the transesterification of soybean oil, and the conversion of soybean oil can reach 63.2% at 70 °C for 8 h.     

Correlation of the deactivation of CoMo/Al2O3 in hydrodesulfurization with surface carbon species

The deactivation of CoMo/Al₂O₃ in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) was investigated under laboratory conditions that allowed the accelerated deposition of coke on the catalyst. The coke deposition was enhanced at low H₂ pressures and when naphthalene was added to the reaction solution. Characterization of deactivated catalysts by elemental analysis (EA) and temperature-programmed oxidation (TPO) identified two types of carbonaceous species deposited on the catalysts, the reactive and the refractory species. The refractory deposit, or hard coke, was a major contributor to the deactivation and, therefore, the amounts of hard coke present on the catalyst determined the overall activity. A correlation was established in this study between the activity and the amounts of deposited hard coke based on the results of accelerated deactivation treatment. A similar relation was also observed between the two parameters when the catalyst was used in an industrial process for long periods. The above findings suggest that the reaction periods of two different scales, i.e., in laboratory and industrial processes, can be correlated with each other based on the amounts of hard coke when coking is the major mechanism of catalyst deactivation.