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.     

Adsorption of NO and NO2 on ceria–zirconia of composition Ce0.69Zr0.31O2: A DRIFTS study

In this study, the nature of surface intermediates generated by adsorption of NO and NO₂ on a commercial ceria–zirconia powder of composition Ce_0.69Zr_0.31O₂ was investigated using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The conditions of occurrence of the main adsorbed species, i.e. nitrites and nitrates, are studied semi-quantitatively as a function of catalyst pre-treatment and/or type of adsorbed NO_x molecule. On the partially reduced ceria–zirconia, the primary role of NO_x is to re-oxidize the surface via adsorption/decomposition on reduced sites. By contrast, the formation of nitrites and nitrates readily occurs on oxidized surfaces, the latter kind of species being strongly promoted in the case of NO₂ adsorption only.     

CO2 reforming of CH4 over stabilized mesoporous Ni-CaO-ZrO2 composites

Mesoporous Ni-CaO-ZrO₂ nanocomposites with high thermal stability were designed and employed in the CO₂/CH₄ reforming. The nanocomposites with appropriate Ni/Ca/Zr molar ratios exhibited excellent activity and prominent coking resistivity. The Ni crystallites were effectively controlled under the critical size for coke formation in such nanocomposites. It was found that low Ni content resulted in high metal dispersion and good catalytic performance. Moreover, the basicity of the matrices improved the chemisorption of CO₂ and promoted the gasification of deposited coke on the catalyst.     

DRIFT study of the interaction of NO and O2 with the surface of Ce0.62Zr0.38O2 as deNOx catalyst

Gas–solid interactions and surface intermediates evolution after NO adsorption onto calcined Ce_0.62Zr_0.38O₂ were investigated. The results of adsorption and temperature-programmed desorption of NO were explained using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) coupled with temperature-programmed experiments in environmental cell. Surface NO-containing species such as nitrites and nitrates were identified during evolution of NO on the surface of Ce_0.62Zr_0.38O₂ solid solution at low and high temperature. The ceria–zirconia solid solution was found to be active in deNO_x reaction in the presence of a “toluene, propene and propane” mixture.     

Kinetic modeling of storage and reduction with different reducing agents (CO, H2, and C2 H4) on a Pt–Ba/-Al2O3 catalyst in the presence of CO2 and H2O

In this paper a global reaction kinetic model is used to understand and describe the NO_x storage/reduction process in the presence of CO₂ and H₂O. Experiments have been performed in a packed bed reactor with a Pt–Ba/γ-Al₂O₃ powder catalyst (1 wt% Pt and 30 wt% Ba) with different lean/rich cycle timings at different temperatures (200, 250, and ) and using different reductants (H₂, CO, and C₂H₄). Model simulations and experimental results are compared. H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. The rate of NO storage increases with temperature. The reduction of stored NO with H₂ is complete for all investigated temperatures. At temperatures above , the water gas shift (WGS) reaction takes place and H₂ acts as reductant instead of CO. At , CO and C₂H₄ are not able to completely regenerate the catalyst. At the higher temperatures, C₂H₄ is capable of reducing all the stored NO, although C₂H₄ poisons the Pt sites by carbon decomposition at . The model adequately describes the NO breakthrough profile during 100 min lean exposure as well as the subsequent release and reduction of the stored NO. Further, the model is capable of simulating transient reactor experiments with 240 s lean and 60 s rich cycle timings.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.     

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.     

EPR studies on NO interaction with MoOx/t-ZrO2 catalysts obtained by slurry deposition

Variable temperature adsorption of nitric oxide on MoO₃ supported on tetragonal zirconia (MoO_x/t-ZrO₂), obtained by slurry deposition, was investigated by EPR spectroscopy. The influence of molybdenum loading and co-adsorbed oxygen on the adsorption process of NO was elucidated. Particular attention was devoted to redox character of NO activation. Another important aspect concerned is the nature of surface nitrosyl complexes of molybdenum and their thermal stability. The role of oxygen in NO transformation over catalyst surface was also discussed.     

CoAl2O4 spinel catalyst for soot combustion with NOx/O2

Mesoporous and nanosized cobalt aluminate spinel with high specific surface area was prepared using microwave assisted glycothermal method and used as soot combustion catalyst in a NO_x + O₂ stream. For comparison, zinc aluminate spinel and alumina supported platinum catalysts were prepared and tested. All samples were characterised using XRD, (HR)TEM, N₂ adsorption–desorption measurements. The CoAl₂O₄ spinel was able to oxidise soot as fast as the reference Pt/Al₂O₃ catalyst. Its catalytic activity can be attributed to a high NO_x chemisorption on the surface of this spinel, which leads to the fast oxidation of NO to NO₂.     

Oxidation of CH4 over Pd supported on TiO2-doped SiO2: Effect of Ti(IV) loading and influence of SO2

Titania-modified silicas with different weight% of TiO₂ were prepared by sol–gel method and used as supports for Pd (1 wt%) catalysts. The obtained materials were tested in the oxidation of methane under lean conditions in absence and in presence of SO₂. Test reactions were consecutively performed in order to evaluate the thermal stability and poisoning reversibility. Increasing amounts of TiO₂ improved the catalytic activity, with an optimum of the performance for 10 wt% TiO₂ loading. Moreover, the titania-containing catalysts exhibited a superior tolerance towards SO₂ by either adding it to the reactants or feeding it as a pure pretreatment atmosphere at 350 °C. Catalysts were characterized by XPS, XRD, FT-IR and BET measurements. According to the structural and surface analyses, the mixed oxides contained Si–O–Ti linkages which were interpreted as being responsible for the enhanced intrinsic activity of supported PdO with respect to PdO on either pure SiO₂ or pure TiO₂. Moreover, the preferential interaction of the sulfur molecule with TiO₂ and the easy SO_x desorption from high surface area silica were the determining factors for the superior SO₂ tolerance of the TiO₂-doped catalysts.     

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.     

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).     

Selective reduction of NOx by hydrogen and methane in natural gas stationary sources over alumina-supported Pd, Co and Co/Pd catalysts: Part A. On the effect of palladium precursors and catalyst pre-treatment

The aim of the present work is to study the selective reduction of NO_x from natural gas sources. The unburned methane can be used as reductant. Another reductant such as hydrogen can be created in situ, using a microreformer. The results suggest that the NO_x are reduced by H₂ at low temperature, when methane is not activated and at higher temperature the methane is then the main reductant. However, the catalytic behaviour depends on the metal precursor and the catalyst treatment. The most prominent result is obtained on the palladium catalyst prepared from Pd(NH₃)₄(NO₃)₂ precursor. Comparing the reduction and the calcination step in the course of catalyst preparation, one can conclude that calcination lead to the higher activity in deNO_x, since reduced catalysts are oxidized during the deNO_x process.     

Selective reduction of NOx by hydrogen and methane in natural gas stationary sources over alumina supported Pd, Co and Co/Pd catalysts: Part B: On the effect of bimetallic catalyst preparation

The aim of the present work is to study the selective reduction of NO_x from natural gas sources using unburned methane or hydrogen as reducing agents. The results suggest that the NO_x are reduced by H₂ at low temperature, when methane is not activated and at higher temperature the methane is then the main reducing agent. Similar results are obtained for alumina supported palladium and alumina supported cobald-palladium catalysts at low temperature in presence of hydrogen suggesting that the active phase for the reaction NO/H₂ is the palladium. However, at high temperature the higher activity is obtained on bimetallic catalyst. The presence of cobalt enhances the catalytic activity. This result suggests that cobalt and palladium both in cationic form are the active sites when the reducing agent is the methane.     

Monolithic-like TiO2 nanotube supported Ru catalyst for activation of CH4 and CO2 to syngas

Highly-ordered TiO₂ nanotube arrays (TiNTA) were prepared by an electrochemical anodization method and used as the carrier material to load 1 wt.% Ru. The Ru/TiNTA catalyst was then applied to the combination reactions of the partial oxidation of methane reaction (POM) with the carbon dioxide reforming with methane reaction (CRM) for syngas production. In comparison with the commercial TiO₂ powder (P25) supported 1 wt.% Ru catalyst, Ru/TiNTA shows higher activity and much better stability. The superior performance of Ru/TiNTA is attributed to the specific monolithic-like structure and confinement effect of TiNTA.     

Influence of OSC Material on the Behaviour of Metallic Pd Catalysts in C2H4 and CO Oxidation as Well as in NO Reduction

The interaction of CO, C₂H₄, O₂, and NO reaction gas compounds over the metallic Pd/Al₂O₃ and Pd/OSC/Al₂O₃ monoliths was investigated in order to understand the behaviour of OSC material in the oxidation and reduction reactions. FT-IR gas analyser was used for the analysis of the product gas composition. Several activity experiments carried out with dissimilar feedstreams have revealed that the Ce _x Zr_1–x O₂ mixed oxide is an oxygen storage compound, which promotes CO and C₂H₄ oxidation as well as NO reduction in particular at low temperatures.     

An exploratory study of diesel soot oxidation with NO2 and O2 on supported metal oxide catalysts

A number of supported metal oxide catalysts were screened for their catalytic performance for the oxidation of carbon black (CB; a model diesel soot) using NO₂ as the main oxidant. It was found that contact between the carbon and catalyst was a key factor in determining the rate of oxidation by NO₂. Oxides with low melting points, such as Re₂O₇, MoO₃ and V₂O₅ showed higher activities than did Fe₃O₄ and Co₃O₄. The activities of MoO₃ and V₂O₅ on various supporting materials were also examined. MoO₃/SiO₂ was the most active catalyst among the supported MoO₃ examined, whereas, V₂O₅/MCM-41 showed the highest activity among the supported V₂O₅. Different performances of the supported MoO₃ catalysts were explained by the interaction of MoO₃ with the supports: a strong MoO₃/support interaction may result in a poor mobility of MoO₃ and a poor activity for oxidation of carbon by NO₂. The high activity of V₂O₅/MCM-41 was associated with its catalysis of the oxidation of SO₂ by NO₂ to form SO₃, which substantially promotes oxidation of carbon by NO₂. Addition of transition metal oxides or sulfates to supported MoO₃ and V₂O₅ was also investigated. Combining MoO₃ or V₂O₅ with CuO on SiO₂, adding VOSO₄ to MoO₃/SiO₂ or MoO₃/Al₂O₃ and adding TiOSO₄ or CuSO₄ to V₂O₅/Al₂O₃ improved the catalytic performance.     

Vermiculites intercalated with Al2O3 pillars and modified with transition metals as catalysts of DeNOx process

Vermiculites intercalated with alumina pillars and modified with transition metals (Cu, Fe) were studied as catalysts of selective reduction of NO with ammonia. Prior to the pillaring process, a raw vermiculite was treated with a solution of nitric acid and then citric or oxalic acid in order to reduce the overall charge of layers. This modification was necessary for a successful pillaring of the clay. Transition metals (Fe, Cu) were deposited on the surface of the modified vermiculites by an ion-exchange method. The obtained samples were characterized with respect to composition (EPMA), structure (XRD), texture (BET) and chemical nature of deposited transition metal species (UV–vis–DRS). The vermiculite based materials have been found to be active and selective catalysts of the DeNOx process. The Cu-containing samples were catalytically active at lower temperatures than the pillared clays modified with iron. A side reaction of ammonia oxidation by oxygen decreased the effectiveness of the DeNOx process in the high temperature range.     

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.     

Role of vanadium sites in NO and O2 adsorption processes over VOx/CeO2-ZrO2 catalysts – EPR and IR studies

The interaction of NO and O₂ with 5 mol.% of vanadia deposited on Ce_0.10Zr_0.90O₂ and Ce_0.69Zr_0.31O₂ supports by wet impregnation was studied by means of EPR and IR. The supports were structurally characterized by XRD and Raman spectroscopy. Influence of the phase composition of the support on vanadium speciation as well as on surface architecture of the oxovanadium entities was discussed. The NO forms adsorbed on vanadium-containing systems were compared to those observed on bare CeO₂-ZrO₂ supports. The main products appearing on the catalysts surface during the consecutive reaction with NO and O₂ were identified and their thermal evolution was observed. Changes in vanadium speciation accompanying redox processes related to NO and O₂ activation were also observed and discussed.