NOx storage behavior and sulfur-resisting performance of the third-generation NSR catalysts Pt/K/TiO2–ZrO2

The NO_x storage and reduction (NSR) catalysts Pt/K/TiO₂–ZrO₂ were prepared by an impregnation method. The techniques of XRD, NH₃-TPD, CO₂-TPD, H₂-TPR and in situDRIFTS were employed to investigate their NO_x storage behavior and sulfur-resisting performance. It is revealed that the storage capacity and sulfur-resisting ability of these catalysts depend strongly on the calcination temperature of the support. The catalyst with theist support calcined at 500 °C, exhibits the largest specific surface area but the lowest storage capacity. With increasing calcination temperature, the NO_x storage capacity of the catalyst improves greatly, but the sulfur-resisting ability of the catalyst decreases. In situ DRIFTS results show that free nitrate species and bulk sulfates are the main storage and sulfation species, respectively, for all the catalysts studied. The CO₂-TPD results indicate that the decomposition performance of K₂CO₃ is largely determined by the surface property of the TiO₂–ZrO₂ support. The interaction between the surface hydroxyl of the support and K₂CO₃ promotes the decomposition of K₂CO₃ to form –OK groups bound to the support, leading to low NO_x storage capacity but high sulfur-resisting ability, while the interaction between the highly dispersed K₂CO₃ species and Lewis acid sites gives rise to high NO_x storage capacity but decreased sulfur-resisting ability. The optimal calcination temperature of TiO₂–ZrO₂ support is 650 °C.     

Comparison Between a Pt–Rh/Ba/Al2O3 and a Newly Formulated NOX-Trap Catalysts Under Alternate Lean–Rich Flows

In situ FT-IR spectroscopy coupled with mass spectrometry have been used to study the mechanism of nitrates formation and reduction over a common Pt–Rh/Ba/Al₂O₃ NO _x storage catalyst, compared with a different alumina-based compound.The experimental device used consists of a transmission reactor cell (having a very small dead volume) dedicated to the evolution of surface species, and of a mass spectrometer combined with a FT-IR micro-cell for gas analysis, allowing time resolved analysis in stationary and transient conditions.At the first time the nitration properties of the catalysts under a lean flow have been studied in the appropriate temperature window (473–673 K). The dynamics of nitrates formation has been pointed out, as well as the different coordination sites on the compounds surface. Then the catalysts have been alternatively exposed to rich and lean flows very close to the real exhaust composition. This has allowed the identification of reduction pathway, active sites, intermediate species and by-products for NO _X -trap reaction. In particular, we have differentiated the role of the support and of the noble metal in the mechanism, as well as of isocyanate adspecies and ammonia among the detected species. The very high NO _X storage properties and the selectivity (near 100%) in nitrogen of the newly designed catalyst have been pointed out.     

Methanol interaction with NO2: An attempt to identify intermediate compounds in CH4-SCR of NO with Co/Pd-HFER catalyst

The objective of this work is the study of fundamental common aspects of NO_x catalytic reduction over a Co/Pd-HFER zeolite catalyst, using methanol or methane as reducing agent. Temperature Programmed Surface Reaction (TPSR) studies were performed with reactant mixtures comprising NO₂ and one of the reducing agents.The formation of formaldehyde was detected in both studied reactions (NO₂–CH₄ and NO₂–CH₃OH) in the temperature range between 100 and 220 °C. At higher temperature, when the NO_x reduction process effectively begins, formaldehyde starts to be consumed.Using methanol as reducing agent, nitromethane and nitrosomethane, are detected. At 300 °C these species are consumed and cyanides and iso-cyanides formation occurs. On the contrary, with methane, these last species were not detected; however, there are strong evidences for CH₃NO and CH₃NO₂ formation.Thus, using methanol or methane, similar phenomena were detected. In both cases, common intermediary species seem to play an important role in the NO_x reduction process to N₂.These results suggest that methanol can be considered as a reaction intermediate species in the mechanism of the reduction of NO₂ with methane, over cobalt/palladium-based ferrierite catalysts.     

Influence of Hydrocarbon Chemisorption on the NOx Adspecies over Supported Noble-Metal Catalysts

In situ and time-resolved DRIFT methods were used to monitor the change in NO _x adspecies on Pt(1%)–TiO₂ and Rh(1%)–TiO₂ catalysts during interaction with propene with the aim to determine whether or not propene chemisorption and interaction with the catalyst induces a change in the nature of the NO _x adspecies prior to their reduction. The nature of NO _x adspecies produced by interaction of the NO + O₂/He feed with the catalyst is different on Pt- and Rh–TiO₂ (in the Pt–TiO₂ catalyst the IR more intense adspecies are nitrate, while in the Rh–TiO₂ catalyst nitrosyl species are the IR more intense), but modification of the nature of the adspecies prior to their conversion is observed in both cases. The interpretation of the data provides indication about the nature of the reactive NO _x species and the presence of multiple pathways in the mechanism of their conversion.     

Transient Surface Processes of Storage and Conversion of NOx Species on Pt–Me/Al2O3 Catalysts (Me = Ba,Ce, Cu)

The transient reactivity and surface phenomena of storage and conversion of NO _x species on Pt(1%)–Me/Al₂O₃ catalysts, where Me = Ba, Ce and Cu, were studied by the RWF (rectangular wavefront) method. The Me component has a relevant influence on the processes of surface storage and transformation. The reduction of NO _x by propene in the presence of oxygen is promoted by adding Cu to a Pt/Al₂O₃ catalyst, while cerium promotes transient conversion of NO in the absence of propene, but inhibits the reduction of NO _x in the presence of propene. Copper is suggested to be a promising element to add together with Ba for new NO _x storage-reduction catalysts due to its capacity to act both as a storage element and as promoter for NO _x reduction.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

Evaluation of a NOx Reduction System on an Engine Rig Under Stationary Operation

The NO _x storage and reduction approach was applied on a full-scale engine rig under stationary operation. NO _x reduction experiments were performed and a catalyst model developed and tested. The exhaust system was equipped with a bypass system. A NO _x reduction of 25–53% was achieved. At low temperature, higher values were reached when the exhaust gas bypass was longer than the injection period.     

Preparation of Ceria-Zeolite Catalysts by Different Techniques and Its Effect on Selective Catalytic Reduction of NO with NH3 at High Space Velocities

Several zeolite-based catalysts containing Ce³⁺ and/or CeO₂ were prepared by a variety of catalyst preparation techniques like ion exchange, solid-state ion exchange, impregnation and physical mixing and are characterised. Selective catalytic reduction was evaluated using simulated exhaust gas containing NO _x , NH₃, O₂ and H₂O at high space velocities (>180000 h^–1) in the temperature window 150–600 °C. The activity and selectivity in NO _x reduction was found to strongly depend on the charge compensating ions, crystallite size of the zeolite and CeO₂ content in the catalyst. CeO₂ mixed with zeolite having H⁺ or Ce³⁺ co-cations showed benificial effect and increased the NO _x conversion and selectivity. Among the different zeolite materials studied, the structure and the strength and amount of Brønsted acidity did not influence the NO _x conversion.     

Effect of Iron Addition on the Durability of Pd–Pt-Loaded Sulfated Zirconia for the Selective Reduction of Nitrogen Oxides by Methane

The effects of adding iron to Pd–Pt/sulfated zirconia (SZ) on the selective NO _x reduction by methane were examined based on durability tests under conditions simulating natural gas combustion exhaust. While Pd–Pt/SZ was severely deactivated at 500 °C, Pd–Pt/Fe-SZ maintained a NO _x conversion higher than 70% for over 2400 h under the same conditions. Methane conversion on Pd–Pt/Fe-SZ was significantly lower than that on Pd–Pt/SZ. XRD analysis of fresh and used catalysts showed that a part of the SZ had transformed to monoclinic ZrO₂ and that adding Fe suppressed the transformation. These results suggested that the improvement in NO _x conversion by adding Fe was due to the suppression of methane combustion and the stabilization of SZ against transformation to ZrO₂.     

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.     

Simulation of SCR equipped vehicles using iron-zeolite catalysts

Iron-catalysts, based on ZSM-5 (FeZSM5) and Cuban natural Mordenite (FeMORD) zeolites have been prepared by a conventional ion-exchange method and their catalytic activity in the selective catalytic reduction (SCR) of NO with ammonia was studied in the presence of H₂O and SO₂. A commercial SCR catalyst (CATCO) based on V₂O₅–WO₃–TiO₂, was also studied as a reference. This paper presents the experimental results of using these catalysts without toxic vanadium and also exploits a neural network-based approach to predict NO_x conversion efficiency of three SCR catalysts. The mathematical functions derived have been integrated into a numerical model to simulate diesel road vehicles equipped with SCR catalysts such as those studied here. The main results indicate that despite toxic vanadium and N₂O formation, CATCO shows better NO_x conversion efficiencies. However, FeMORD does not produce N₂O and performs better than the FeZSM5. The simulation results on real cycles show lower level of NO_x for heavy-duty and light-duty diesel vehicles compared with homologation load cycles.     

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.     

NOx adsorption and diesel soot combustion over La2O3 supported catalysts containing K, Rh and Pt

In this work we report results of NOx adsorption and diesel soot combustion on a noble metal promoted K/La₂O₃ catalyst. The fresh-unpromoted solid is a complex mixture of hydroxide and carbonate compounds, but the addition of Rh favors the preferential formation of lanthanum oxycarbonate during the calcination step. K/La₂O₃ adsorbs NOx through the formation of La and K nitrate species when the solid is treated in NO + O₂ between 70 and 490 °C. Nitrates are stable in the same temperature range under helium flow. However, they become unstable at ca. 360 °C when either Rh and/or Pt are present, the effect of Rh being more pronounced. Nitrates decompose under different atmospheres: NO + O₂, He and H₂. The effect of Rh might be to form a thermally unstable complex (Rh–NO⁺) which takes part both in the formation of the nitrates when the catalyst is exposed to NOx and in the nitrates decomposition at higher temperatures. Regarding soot combustion, nitrates react with soot with a temperature of maximun reaction rate of ca. 370 °C, under tight contact conditions. This temperature is not affected by the presence of Rh, which indicates that the stability of nitrates has little effect on their reaction with soot.     

Low-temperature catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

MnO_x–CeO₂ mixed oxide catalysts prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of chlorinated aromatic volatile organic compounds (CVOCs). MnO_x–CeO₂ catalysts with the different ratio of Mn/Ce + Mn were found to possess high catalytic activity for catalytic combustion of CB, and MnO_x(0.86)–CeO₂ was the most active catalyst, on which the complete combustion temperature (T_90%) of chlorobenzene was 236 °C. The stability of MnO_x–CeO₂ catalysts in the CB combustion was investigated. MnO_x–CeO₂ catalysts with high Mn/Ce + Mn ratios present high stable activity, which is related to their high ability to remove Cl species adsorbed and a large amount of active surface oxygen.     

Comparative NOx Reduction Behavior of Pt, Pd, and Rh Supported Catalysts in Simulated Exhaust Gases as a Function of Oxygen Concentration

NO _x reduction activity on Pt and Pd catalysts had a maximum for S value as stoichiometry number at a fixed temperature, and the S value at the maximum NO _x conversion increased with decreasing temperature. NO _x conversion on Rh catalyst increased with decreasing S value, but independent of temperature. As for the effect of HC on NO _x reduction behavior, it was concluded that, for Pt and Pd catalysts, HC adsorbs strongly on the catalysts surface to cause the self-inhibition. Increasing O₂ concentration lead to oxidation of HC, but decreased the value of NO/O₂ ratio. The balance point of the two factors generated a maximum NO _x conversion. For Rh catalyst, the strongly adsorbed oxygen is more reactive with decreasing S value, and thus NO _x conversion is increased.     

Methane activation by NO2 on Co loaded SBA-15 catalysts: The effect of mesopores (length, diameter) on the catalytic activity

In a general model of “three-function deNO_x” catalyst, the partial oxidation of methane by NO₂ is an important step (CH₄ + NO₂ → C_xH_yO_z + NO). To study the effect of the length and diameter, in the mesopores of SBA-15, we have synthesized catalysts with 3 wt.% cobalt supported on SBA-15, with differences in length and diameter of channels. Three different cobalt species were detected on all catalysts. We demonstrated by TPSR experiments that the activity of cobalt/SBA-15 catalysts is affected by the length, the diameter and connections between mesopores of the SBA-15 supports. We show that by changing textural properties of silica support the temperature of 100% conversion of NO₂ into NO can decrease by more than 100 °C.     

NOx Abatement by Catalytic Traps: On the Mechanism of NOx Trapping Under Automotive Conditions

NO _x adsorption was measured with a barium based NO_x storage catalyst at an engine bench equipped with a lean burn gasoline direct injection engine (GDI). In order to study the influence of gas phase NO₂ on the NO_x storage efficiency two different pre-catalysts were used: One with excellent NO oxidation activity to produce a high NO₂ concentration and another pre-catalyst without NO oxidation activity and therefore high NO concentration at the NO _x storage catalyst inlet. Both pre-catalyst had excellent HC and CO conversion efficiency and therefore the CO and HC concentration at the NO _x storage catalyst inlet was practically zero. No lean NO _x reduction was observed. Under that conditions, experiments with NO _x storage catalysts of different length show that a high NO₂ inlet concentration did not enhance the NO _x storage efficiency. Moreover, we observed reduction of NO₂ to NO over the NO_x storage catalyst. However, in presence of a high NO inlet concentration NO₂ formation was observed which may proceed parallel to NO _x storage.     

NOx Adsorption Study over Pt–Ba/Alumina Catalysts: FT-IR and Reactivity Study

The NO _x storage process over Ba/Al₂O₃ and Pt–Ba/Al₂O₃ NSR catalysts has been analyzed in this study by performing experiments at 350 °C with NO₂ and NO/O₂ mixtures using different complementary techniques (Transient Response Method, in situ FT–IR and DRIFT spectroscopies). The collected data suggest that over the Pt–Ba/Al₂O₃ catalyst the NO _x storage process from NO/O₂ mixtures occurs forming at first nitrite species, which progressively evolve to nitrates. In addition, a parallel nitrate formation via disproportionation of NO₂ (formed upon NO oxidation) cannot be excluded.     

Advanced De-SOx catalyst: Mixed solid solution spinels with cerium oxide

Mixed solid solution spinels impregnated with cerium, Ce/MgO·MgAl_2-xM_xO₄ (M=Fe, V, Cr, x≤0.4), were studied for controlling the SO_x emission from the fluid catalytic cracking (FCC) regenerator. An insufficient sulfur release problem inherent to the earlier De---SO_x catalyst, Ce/MgO·MgAl₂O₄, was effectively overcome by incorporating a transition metal into the spinel structure. Studies of the SO_x pick-up, temperature profile for the sulfate reduction, the thermal analysis, and the De---SO_x cycle test in the batch as well as the automated continuous reactor are discussed to define the role of a transition metal in the mixed spinels for the De---SO_x performance. These advanced De---SO_x catalysts have led to a commercial success for the simultaneous control of SO_x and NO_x emissions from the FCC regenerator.     

Ceria–zirconia-supported rhodium catalyst for NOx reduction from coal combustion flue gases

The catalytic activities of ceria–zirconia mixed oxides Ce_xZr_1−xO₂ (x = 0.17, 0.62 and 0.8) rhodium catalysts were determined by isothermal steady-state experiments using a representative mixture of exhaust gases of coal combustion. Results show that all supports are active in deNO_x reaction in the presence of the mentioned gas mixture. However, their catalytic activity varies with the content of cerium and goes through a maximum for x = 0.62, leading to 27% NO_x consumption. The effect of rhodium on Ce_0.62Zr_0.38O₂ considerably improves the catalytic activity during the deNO_x process assisted by hydrocarbons. The rhodium addition decreases by about 34 °C the temperature of NO_x consumption, which goes up to 57%. A mechanism of hydrocarbon (HC) assisted reduction of NO is proposed on ceria–zirconia-supported rhodium catalysts. This mechanism is divided in three catalytic cycles involving (i) the oxidation of NO into NO₂, (ii) the reaction of NO₂ and the hydrocarbons leading to RNO_x species and C_xH_yO_z, and finally (iii) the decomposition of NO assisted by these latter C_xH_yO_z species.