Production of hydrogen via partial oxidation of methanol over Au/TiO2 catalysts

Selective production of hydrogen by partial oxidation of methanol (CH₃OH + (1/2)O₂ → 2H₂ + CO₂) over Au/TiO₂ catalysts, prepared by a deposition–precipitation method, was studied. The catalysts were characterized by XRD, TEM, and XPS analyses. TEM observations show that the Au/TiO₂ catalysts exhibit hemispherical gold particles, which are strongly attached to the metal oxide support at their flat planes. The size of the gold particles decreases from 3.5 to 1.9 nm during preparation of the catalysts with the rise in pH from 6 to 9 and increases from 2.9 to 4.3 nm with the rise in calcination temperature up to 673 K. XPS analyses demonstrate that in uncalcined catalysts gold existed in three different states: i.e., metallic gold (Au⁰), non-metallic gold (Au^δ+) and Au₂O₃, and in catalysts calcined at 573 K only in metallic state. The catalytic activity is strongly dependent on the gold particle size. The catalyst precipitated at pH 8 and uncalcined catalysts show the highest activity for hydrogen generation. The partial pressure of oxygen plays an important role in determining the product distribution. There is no carbon monoxide detected when the O₂/CH₃OH molar ratio in the feed is 0.3. Both hydrogen selectivity and methanol conversion increase with increasing the reaction temperature. The reaction pathway is suggested to consist of consecutive methanol combustion, partial oxidation and steam reforming.     

CH4/CO2 reforming over La2NiO4 and 10%NiO/CeO2–La2O3 catalysts under the condition of supersonic jet expansion via cavity ring-down spectroscopic analysis

CH₄/CO₂ reforming over La₂NiO₄ and 10%NiO/CeO₂–La₂O₃ catalysts under the condition of supersonic jet expansion was studied via direct monitoring of the reactants and products using the sensitive technique of cavity ring-down spectroscopy. Vibration–rotational absorption lines of CH₄, H₂O, CO₂ and CO molecules were recorded in the near infrared spectral region. Our results indicated that La₂NiO₄ is superior to 10%NiO/CeO₂–La₂O₃ in performance. In addition, we observed enhanced reverse-water-gas-shift reaction at augmented reaction temperature. The formation of reaction intermediates was also investigated by means of time-of-flight mass spectrometry and there was the detection of CH_x⁺, OH⁺ and H⁺ species.     

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

Conversion of NO_x with reducing agents H₂, CO and CH₄, with and without O₂, H₂O, and CO₂ were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO_x to N₂ conversion with H₂ and CO (>90% conversion and N₂ selectivity) range under lean conditions. The formation of N₂O is absent in the presence of both H₂ and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H₂ and CO at 450–500 K. The positive effect of cerium is significant in the case of H₂ and CH₄ reducing agent but is less obvious with H₂/CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH₄, 500 ppm NO, 5% O₂, 10% H₂O (0–1% H₂), N₂ balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO_x reduction with H₂, CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K.     

Partial oxidation of ethanol on Ru/Y2O3 and Pd/Y2O3 catalysts for hydrogen production

The partial oxidation of ethanol was investigated over Ru and Pd catalysts supported onto yttria over a wide range of temperatures (473–1073 K). The product distributions obtained over these catalytic systems were correlated with diffuse reflectance infrared spectroscopy analyses (DRIFTS). Results showed that reaction route depended strongly on the type of metal. The decomposition of ethoxy species to CH₄ and CO or oxidation to CO₂ was promoted by Pd, and the acetaldehyde desorption was predominant over Ru in the low temperature region. Furthermore, the acetate and carbonate formation prevailed over Pd, which explained the lower acetaldehyde selectivity. The presence of CH₄ and CO₂ at high temperature is assigned to the decomposition of acetate species via carbonates over Pd-based catalysts. Ru was more suitable system for H₂ production than Pd by achieving a selectivity of about 59%.     

The reactions of ethanol over M/CeO2 catalysts: Evidence of carbon–carbon bond dissociation at low temperatures over Rh/CeO2

The reactions of ethanol over Rh/CeO₂ have been investigated using the techniques of temperature programmed desorption (TPD) and FT-IR spectroscopy, in addition to steady state catalytic tests. A comparison with previous studies of ethanol adsorption over Pd/CeO₂ [J. Catal. 186 (1999) 279] and Pt/CeO₂ [J. Catal. 191 (2000) 30] catalysts is presented. The apparent activation energy for the reaction was 49, 40, and 43 kJ mol⁻¹ for Rh/CeO₂, Pd/CeO₂ and Pt/CeO_2, respectively, while the turnover number (TON) at 400 K was 5.9, 8.6 and 2.6, respectively. Surface compositions of catalysts were characterised by XPS. A decrease of the atomic O(1s)/Ce(3d) ratio of the CeO₂ support indicates its partial reduction upon addition of the noble metal. The extent of reduction per metal atom was in the following order: Pt>Pd>Rh. FT-IR and TPD studies have shown that dehydrogenation of ethanol to acetaldehyde occurred over Pd/CeO₂, Pt/CeO₂ and Rh/CeO₂. Moreover, Rh/CeO₂ readily dissociated the C–C bond of ethanol at room temperature to form adsorbed CO (IR bands at 1904–2091 cm⁻¹). This was corroborated by the low desorption temperature of CH₄ over Rh/CeO₂ (450 K) when compared to that of Pd/CeO₂ (550 K) or Pt/CeO₂ (585 K).     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

Preparation and characterization of LaFe1−xMgxO3/Al2O3/FeCrAl: Catalytic properties in methane combustion

MnO_x–CeO₂ mixed oxides prepared by sol–gel method, coprecipitation method and modified coprecipitation method were investigated for the complete oxidation of formaldehyde. Structure analysis by H₂-TPR and XPS revealed that there were more Mn⁴⁺ species and richer lattice oxygen on the surface of the catalyst prepared by the modified coprecipitation method than those of the catalysts prepared by sol–gel and coprecipitation methods, resulting in much higher catalytic activity toward complete oxidation of formaldehyde. The effect of calcination temperature on the structural features and catalytic behavior of the MnO_x–CeO₂ mixed oxides prepared by the modified coprecipitation was further examined, and the catalyst calcined at 773 K showed 100% formaldehyde conversion at a temperature as low as 373 K. For the samples calcined below 773 K, no any diffraction peak corresponding to manganese oxides could be detected by XRD measurement due to the formation of MnO_x–CeO₂ solid solution. While the diffraction peaks corresponding to MnO₂ phase in the samples calcined above 773 K were clearly observed, indicating the occurrence of phase segregation between MnO₂ and CeO₂. Accordingly, it was supposed that the strong interaction between MnO_x and CeO₂, which depends on the preparation route and the calcination temperature, played a crucial role in determining the catalytic activity toward the complete oxidation of formaldehyde.     

Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios

A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO₂ in the flue gases from fossil fuel-based power plants without CO₂ separation [C. Song, Chemical Innovation 31 (2001) 21–26]. The proposed tri-reforming process is a synergetic combination of CO₂ reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas). Both experimental testing and computational analysis show that tri-reforming can not only produce synthesis gas (CO + H₂) with desired H₂/CO ratios (1.5–2.0), but also could eliminate carbon formation which is usually a serious problem in the CO₂ reforming of methane. These two advantages have been demonstrated by tri-reforming of CH₄ in a fixed-bed flow reactor at 850 °C with supported nickel catalysts. Over 95% CH₄ conversion and about 80% CO₂ conversion can be achieved in tri-reforming over Ni catalysts supported on an oxide substrate. The type and nature of catalysts have a significant impact on CO₂ conversion in the presence of H₂O and O₂ in tri-reforming in the temperature range of 700–850 °C. Among all the catalysts tested for tri-reforming, their ability to enhance the conversion of CO₂ follows the order of Ni/MgO > Ni/MgO/CeZrO > Ni/CeO₂ ≈ Ni/ZrO₂ ≈ Ni/Al₂O₃ > Ni/CeZrO. The higher CO₂ conversion over Ni/MgO and Ni/MgO/CeZrO in tri-reforming may be related to the interaction of CO₂ with MgO and more interface between Ni and MgO resulting from the formation of NiO/MgO solid solution. Results of catalytic performance tests over Ni/MgO/CeZrO catalysts at 850 °C and 1 atm with different feed compositions confirm the predicted equilibrium conversions based on the thermodynamic analysis for tri-reforming of methane. Kinetics of tri-reforming were also examined. The reaction orders with respect to partial pressures of CO₂ and H₂O are different over Ni/MgO, Ni/MgO/CeZrO, and Ni/Al₂O₃ catalysts for tri-reforming.     

K-, CeO2-, and Mn-promoted Ni/Al2O3 catalysts for stable CO2 reforming of methane

Reforming of methane with carbon dioxide into syngas over Ni/γ-Al₂O₃ catalysts modified by potassium, MnO and CeO₂ was studied. The catalysts were prepared by impregnation technique and were characterized by N₂ adsorption/desorption isotherm, BET surface area, pore volume, and BJH pore size distribution measurements, and by X-ray diffraction and scanning electron microscopy. The performance of these catalysts was evaluated by conducting the reforming reaction in a fixed bed reactor. The coke content of the catalysts was determined by oxidation conducted in a thermo-gravimetric analyzer. Incorporation of potassium and CeO₂ (or MnO) onto the catalyst significantly reduced the coke formation without significantly affecting the methane conversion and hydrogen yield. The stability and the lower amount of coking on promoted catalysts were attributed to partial coverage of the surface of nickel by patches of promoters and to their increased CO₂ adsorption, forming a surface reactive carbonate species. Addition of CeO₂ or MnO reduced the particle size of nickel, thus increasing Ni dispersion. For Ni–K/CeO₂–Al₂O₃ catalysts, the improved stability was further attributed to the oxidative properties of CeO₂. Results of the investigation suggest that stable Ni/Al₂O₃ catalysts for the carbon dioxide reforming of methane can be prepared by addition of both potassium and CeO₂ (or MnO) as promoters.     

CO oxidation at low temperature over Pd supported on CeO2-TiO2 composite oxide

Low temperature CO oxidation was carried out over CeO₂-TiO₂ composite oxide and thereon supported Pd catalysts. The effects of Ce/Ti ratio and pre-treatments of calcination and reduction on the catalytic behaviour were investigated. The CO oxidation starts at about 220 °C over CeO₂-TiO₂ and the pre-reduction treatment has little influence on the catalytic activity. Pd supported on CeO₂-TiO₂ (Pd/CeO₂-TiO₂) exhibits high activity for CO oxidation and a complete conversion of CO to CO₂ can be achieved even at ambient temperature, which suggests a synergistic effect between Pd and CeO₂-TiO₂. The activity and stability of Pd/CeO₂-TiO₂ can be further improved by the pre-reduction treatment. Ce/Ti ratio influences the catalytic behaviour significantly; the catalyst Pd/CeO₂-TiO₂ with a Ce/Ti mole ratio of 0.20 (Pd/Ce20Ti) owns the highest activity and stability, which suggests an optimization of the Pd-Ce-Ti interaction in Pd/Ce20Ti. The calcined Pd/CeO₂-TiO₂ with a Ce/Ti mole ratio higher than 0.10 shows a distorted light-off profile with the temperature, which implies an alternation of the reaction mechanism with increasing temperature.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Photocatalytic conversion of CH4 and CO2 to oxygenated compounds over Cu/CdS–TiO2/SiO2 catalyst

Coupled semiconductor (CS) Cu/CdS–TiO₂/SiO₂ photocatalyst was prepared using a mutli-step impregnation method. Its optical property was characterized by UV–vis spectra. BET, XRD, Raman and IR were used to study the structure of the photocatalyst. Fine CdS was found dispersed over the surface of anatase TiO₂/SiO₂ substrate. Chemisorption and IR analysis showed methane absorbed in the molecular state interacted weakly with the surface of catalyst, and the interaction of CO₂ with CS produced various forms of absorbed CO₂ species that were primarily present in the form of formate, bidentate and linear absorption species. Photocatalytic direct conversion of CH₄ and CO₂ was performed under the operation conditions: 373 K, 1:1 of CO₂/CH₄, 1 atm, space velocity of 200 h⁻¹ and UV intensity of 20.0 mW/cm². The conversion was 1.47% for CH₄ and 0.74% for CO₂ with a selectivity of acetone up to 92.3%. The reaction mechanisms were proposed based on the experimental observations.     

CO2 reforming of methane to syngas over highly active and stable Pt/MgO catalysts

Pt/MgO catalysts were prepared by wet impregnation. At 800 °C and atmospheric pressure, Pt/MgO catalysts exhibited a high stability at high gas hourly space velocity of 36,000 ml/g h with a CH₄/CO₂ ratio of 1.0. During 72 h time on stream, the conversion of CH₄ and CO₂ remained almost constant, at about 88% and 90%, respectively. There was no loss of Pt. After reaction, the XRD peaks of MgO became broader, indicating amorphization of MgO, which was supported by TEM results. XPS indicated that the reforming reaction had little influence on Pt. CO₂-TPSR results showed that some carbon deposition occurred under stoichiometric feed of CH₄ and CO₂, but it did not result in the deactivation of the catalyst. The deposited carbon came mainly from the decomposition of methane.     

The oxidizing role of CO2 at mild temperature on ceria-based catalysts

For thermodynamic reasons, CO₂ has always been considered as inert at mild reaction temperatures (300 °C). In this study, we show that CO₂ may be used as a valuable compound for the catalytic combustion of methane (CCM), if ceria-based materials are used as support for the palladium active phase. Adding CO₂ in the feed significantly improves performances of ceria-zirconia supported catalysts. On the contrary, catalytic performances are inhibited on Pd/γ-Al₂O₃. Inhibition can be avoided by mixing the Pd/γ-Al₂O₃ catalyst with some CeO₂ evidencing cooperation phenomena between both catalysts. In situ DRIFTS experiments show that the inhibition of the alumina-supported catalyst is not due to formation of carbonates species. After an in situ reducing pre-treatment, pure CO₂ is able to rapidly oxidize reduced Pd/Ce_0.21Zr_0.79O₂ catalyst at 300 °C. Dissociation of CO₂ on Ce_0.21Zr_0.79O₂ would be responsible for the oxidation process. Thus, CO₂ helps in replenishing the O reservoir (OSC) of the Ce-Zr-O support which is normally consumed by reductants such as CH₄, H₂ or other HC's. XPS experiments show enrichment in oxygen species bound to Ce (Low BE O1s) on the surface of ceria-zirconia when working in the presence of CO₂. Implications of these results on the behavior of ceria-containing catalysts can be important for practical applications, e.g., in automotive exhaust catalysis.     

Potential of zeolite supported rhodium catalysts for the CO2 reforming of CH4

Zeolite Y supported rhodium catalysts were prepared by ion-exchange starting from an aqueous solution of [Rh[(NH₃)₅Cl]Cl₂·6H₂0]. Previous work in this laboratory had shown that this procedure results in a Rh dispersion of near 100%. The catalysts were tested for their activity in the CO₂ reforming of CH₄. They were found to combine extraordinary stability with high activity and selectivity. At 923 K, 90 mol-% of the CH₄ was converted giving a H₂/CO ratio near unity. A weight loading of 0.5 to 0.93% Rh gives the highest turnover frequencies. Thermodynamic equilibrium is reached near 873 K. With a given Rh loading, the zeolite supports are superior to amorphous supports and NaY is superior to the HY. No deactivation was observed in tests of 30 h time on stream at atmospheric pressure or after repeated thermal cycles. No coke deposition was detected by temperature programmed oxidation of used catalysts. Temperature programmed reduction indicates the presence of three discernible Rh species.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

The effect of CeO2 structure on the activity of supported Pd catalysts used for methane steam reforming

Palladium (Pd) supported on CeO₂-promoted γ-Al₂O₃ with various CeO₂ (ceria) crystallinities, were used as catalysts in the methane steam reforming reaction. X-ray diffraction (XRD) analysis, FTIR spectroscopy of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) were employed to characterize the samples in terms of Pd and CeO₂ structure and dispersion on the γ-Al₂O₃ support. These results were correlated with the observed catalytic activity and deactivation process. Arrhenius plots at steady-state conditions are presented as a function of CeO₂ structure. Pd is present on the oxidized CeO₂-promoted catalysts as Pd⁰, Pd⁺ and Pd²⁺, at ratios strongly dependent on CeO₂ structure. XRD measurements indicated that Pd is well dispersed (particles <2 nm) on crystalline CeO₂ and is agglomerated as large clusters (particles in 10–20 nm range) on amorphous CeO₂. FTIR spectra of adsorbed CO revealed that after pre-treatment under H₂ or in the presence of amorphous CeO₂, partial encapsulation of Pd particles occurs. CeO₂ structure influences the CH₄ steam reforming reaction rates. Crystalline CeO₂ and dispersed Pd favor high reaction rates (low activation energy). The presence of CeO₂ as a promoter conferred high catalytic activity to the alumina-supported Pd catalysts. The catalytic activity is significantly lower on Pd/γ-Al₂O₃ or on amorphous (reduced) CeO₂/Al₂O₃ catalysts. The reaction rates are two orders of magnitude higher on Pd/CeO₂/γ-Al₂O₃ than on Pd/γ-Al₂O₃, which is attributed to a catalytic synergism between Pd and CeO₂. The low rates on the reduced Pd/CeO₂/Al₂O₃ catalysts can be correlated with the loss of Pd sites through encapsulation or particle agglomeration, a process found mostly irreversible after catalyst regeneration.     

SAPO-34 membranes for CO2/CH4 separations: Effect of Si/Al ratio

Silicoaluminophosphate (SAPO) membranes with Si/Al gel ratios from 0.05 to 0.3 were synthesized by in situ crystallization onto porous, tubular stainless steel support. Pure SAPO-34 membranes were obtained when the Si/Al ratio was 0.15 or higher. The adsorbate polarizability correlated with the adsorption capacity on SAPO-34, and the amounts of gases adsorbed were in the order: CO₂ > CH₄ > N₂ > H₂. The Si/Al ratio did not affect the pore volume significantly, but it changed the CO₂ and CH₄ adsorption equilibrium constants. The SAPO-34 membranes effectively separated CO₂ from CH₄ for feed pressures up to 7 MPa. At 295 K, for a pressure drop of 138 kPa and a 50/50 feed, the CO₂/CH₄ selectivity was 170 for a membrane with a Si/Al gel ratio of 0.15. At 7 MPa, the CO₂/CH₄ selectivity was 100 and the CO₂ permeance was 4 × 10⁻⁸ mol/(m² · s · Pa) at 295 K. This membrane was also separated CO₂/N₂ (selectivity = 21) and H₂/CH₄ (selectivity = 32) mixtures at 295 K and a pressure drop of 138 kPa. Competitive adsorption and difference in diffusivities are responsible for CO₂/CH₄ and CO₂/N₂ separations, whereas the H₂/CH₄ separation was due to diffusivity differences. For a membrane with Si/Al gel ratio of 0.1, a mixture of SAPO-34 and SAPO-5 formed, and the CO₂/CH₄ selectivity was lower.     

On the mechanism of model diesel soot-O2 reaction catalysed by Pt-containing La-doped CeO2: A TAP study with isotopic O2

Pt supported on CeO₂ and 10 wt.% La³⁺-doped CeO₂ catalysts have been prepared, characterised and tested for soot oxidation by O₂ in TGA. The reaction mechanism has been studied in a TAP reactor with labelled O₂. Isotopic oxygen exchange between molecular O₂ and ‘O’ on the support/catalyst was observed and soot oxidation is being carried out by lattice oxygen. TAP studies further show that Pt improves O₂ adsorption and, therefore, 5 wt.% Pt-containing catalysts are more active for soot oxidation than the counterpart supports. In addition, CeO₂ doping by La³⁺ leads to an improved support, since La³⁺ stabilises the structure of CeO₂ when calcined at high temperature (1000 °C) and minimises sintering. In addition, La³⁺ improves the Ce⁴⁺/Ce³⁺ reduction as deduced from H₂-TPR experiments and favours oxygen mobility into the lattice. A synergetic effect of Pt and La³⁺ is observed, Pt-containing La³⁺-doped CeO₂ being the most active catalyst for soot oxidation by O₂ among the samples studied.     

SCR of NOx with CH3OH on H-mordenite: mechanism and reaction intermediates

The selective reduction of NO_x over H-mordenite (H-m) was studied using CH₃OH as reducing agent. Results are compared with those obtained with other conventional reducing agents (ethylene and methane), with gas-phase reactions, and with other metal-exchanged mordenites (Cu-mordenite (Cu-m) and Co-mordenite (Co-m)). H-m was found to be an effective catalyst for the SCR of NO_x with CH₃OH. When different reducing agents were compared over H-m, CH₃OH > C₂H₄ > CH₄ was the order according to the maximum NO conversion obtained using 1% of oxygen in the feed. Instead, if selectivity is considered, the order results CH₄ > CH₃OH > C₂H₄. In reaction experiments, two distinct zones defined by two maxima with NO to N₂ conversion are obtained at two different temperatures. A correlation exists between the said zones and the CO : CO₂ ratio. At low temperatures, CO prevails whereas at high temperatures CO₂ prevails. These results indicate that there exist different reaction intermediates. Evidence from reaction experiments, FTIR results, and transient experiments suggest that the reaction mechanism involves formaldehyde and dimethyl ether (DME) as intermediates in the 200–500°C temperature range. The surface interaction between CH₃OH (or its decomposition products) and NO is negligible if compared with NO₂, indicating that the oxidation of NO to NO₂ on acid sites is a fundamental path in this system. Different from other non-oxygenated reductants (methane and ethylene), a gas-phase NO_x initiation effect on hydrocarbon combustion was not observed.