Autothermal Reforming Of Methane Research Articles

CO2-to-methanol: Economic and environmental comparison of emerging and established technologies with dry reforming and methane pyrolysis

This work compares 9 process routes that produce methanol from carbon dioxide using new and established thermochemical and electrochemical technologies. Net CO2 conversion is compared, and process efficiencies are benchmarked using side-by-side process models. New process routes using recently reported catalysts that enable methane pyrolysis (PY), and the dry reforming of methane (DMR) are modeled. Comparison is made with direct CO2 hydrogenation to methanol, the co-electrolysis of water and CO2 using solid oxide electrochemistry, and combinations of process technologies. Both electric heating and fuel switching to hydrogen are considered. Autothermal reforming of methane (ATR) is modeled as the conventional technology for reference. A new thermochemical approach in which CO2 reforming and methane pyrolysis reactions occur in separate reactors, with excess hydrogen produced and combusted for heat, (PY/DMR) was found to have the lowest levelized costs of CO2 mitigation varying from $50.4–53.9/t-CO2 using different electricity carbon intensities and levelized cost of methanol of $295.6/t. Methane pyrolysis offers the most flexible process solutions: it is nearly cost-competitive with reforming today ($295.6/t vs $277.3/t) using fuel switching and would emerge as the most economically viable process ($99.5/t) in future scenarios with very low electricity and natural gas costs and very high emissions penalties starting from 2030. Based on the emission factors from both electricity and natural gas across 195 countries around the world, 53 countries would result in net conversion of CO2 via pyrolysis today after heating, fugitive emissions, and energy use are taken into account.

Comparison of Various Hydrogen Production Technologies from Natural Gas

The article provides an overview of the present condition and immediate future potential in the realm of hydrogen energy technologies. The paper delves into the most renowned approaches for generating hydrogen from natural gas: a) Steam-Methane Reforming (SMR); b) Partial Oxidation (POX); and c) Autothermal Reforming (ATR). Nevertheless, employing these technologies on an industrial scale requires substantial R&D efforts, often on the scale of experimental ventures. The article also examines the global energy landscape, energy sources, the historical discovery of hydrogen, and the various production methods. It addresses the intricacies associated with hydrogen production technologies, with a focal point on the technology of extracting hydrogen from natural gas. Through a comparison of the benefits and drawbacks of each method and, as explicated in the concluding section of the study, several significant insights have been derived. Among the three technologies, SMR, the steam conversion process, boasts the highest hydrogen production rate. Catalytic partial oxidation of methane exhibits the swiftest reaction rate; however, it necessitates the use of pure oxygen, which poses safety concerns. The process of methane auto-thermal reforming requires no external heat and is characterized by minimal energy consumption. Steam reforming of methane emerges as an ecologically sound and scientifically promising avenue, offering high effectiveness. Nevertheless, its deployment on an industrial scale remains to be fully refined. Developing cost-effective catalysts and continuous reactor systems for methane steam conversion technology is essential to rendering it economically viable. In conclusion, there is substantial potential for advancements at hydrogen energy technologies, particularly through refining and integrating these different production methods.

Autothermal Reforming of Methane: A Thermodynamic Study on the Use of Air and Pure Oxygen as Oxidizing Agents in Isothermal and Adiabatic Systems

In this paper, we analyze the autothermal reforming (ATR) of methane through Gibbs energy minimization and entropy maximization methods to analyze isothermic and adiabatic systems, respectively. The software GAMS® 23.9 and the CONOPT3 solver were used to conduct the simulations and thermodynamic analyses in order to determine the equilibrium compositions and equilibrium temperatures of this system. Simulations were performed covering different pressures in the range of 1 to 10 atm, temperatures between 873 and 1073 K, steam/methane ratio was varied in the range of 1.0/1.0 and 2.0/1.0 and oxygen/methane ratios in the feed stream, in the range of 0.5/1.0 to 2.0/1.0. The effect of using pure oxygen or air as oxidizer agent to perform the reaction was also studied. The simulations were carried out in order to maintain the same molar proportions of oxygen as in the simulated cases considering pure oxygen in the reactor feed. The results showed that the formation of hydrogen and synthesis gas increased with temperature, average composition of 71.9% and 56.0% using air and O2, respectively. These results are observed at low molar oxygen ratios (O2/CH4 = 0.5) in the feed. Higher pressures reduced the production of hydrogen and synthesis gas produced during ATR of methane. In general, reductions on the order of 19.7% using O2 and 14.0% using air were observed. It was also verified that the process has autothermicity in all conditions tested and the use of air in relation to pure oxygen favored the compounds of interest, mainly in conditions of higher pressure (10 atm). The mean reductions with increasing temperature in the percentage increase of H2 and syngas using air under 1.5 and 10 atm, at the different O2/CH4 ratios, were 5.3%, 13.8% and 16.5%, respectively. In the same order, these values with the increase of oxygen were 3.6%, 6.4% and 9.1%. The better conditions for the reaction include high temperatures, low pressures and low O2/CH4 ratios, a region in which there is no swelling in terms of the oxygen source used. In addition, with the introduction of air, the final temperature of the system was reduced by 5%, which can help to reduce the negative impacts of high temperatures in reactors during ATR reactions.

A comparative investigation of equimolar Ni-, Ru-, Rh- and Pt-based composite structured catalysts for energy-efficient methane reforming

Hydrogen as an optimal fuel for mobile and local fuel cell-based power generators creates a request for effective on-board fossil fuel transformation to hydrogen-rich syngas. Structured catalysts based on carriers with high thermal conductivity can improve fuel conversion and decrease external heat input to a reformer through intensification of temperature distribution in the reforming processes. In this work, carriers of the structured catalysts were made from metal grids consisting of Fe, Cr, and Al alloy. Aiming to compare a catalytic activity per a one active metal atom four Me/Ce0.75Zr0.25O2/Al2O3/FeCrAlloy (Me = Ni, Ru, Pt, and Rh) catalysts with similar molar content of an active metal were prepared. The catalysts were characterized by transmission (TEM) and scanning electron microscopies (SEM), X-Ray diffraction analysis (XRD), and X-Ray photoelectron spectroscopy (XPS) before and after catalytic tests. Investigation of the catalysts’ effectivities in methane steam reforming (MSR) showed that the performances change in the order Rh > Ru > Pt > Ni. The Rh-based structured catalyst provided thermodynamic equilibrium product distribution of MSR products at a relatively low temperature of 600 °C and high flow rates. Hydrogen content in the syngas obtained in MSR over Rh-based structured catalyst was up to 70.3 vol% at the weight hour space velocity (WHSV) of 290 700 Nml⋅gacc−1⋅h−1. Investigation of methane autothermal reforming (MATR) over Pt- and Rh-based structured catalysts at 700 °C approved better performances of the Pt-based catalyst for this process. The syngas obtained in MATR over the Pt-based catalyst contained up to ∼ 40 vol% of H2 and 7.4 vol% of CO with a H2/CO molar ratio of ca. 5.5. The optimal conditions for MATR over the Pt-based catalyst were selected and the catalyst stability in long-term reforming was approved. The developed mathematical model for the description of MATR over Pt-based catalyst correlates well with the experimental data and can be used for scale-up of the process.

The effect of CO2 feeding on syngas quality in autothermal reforming of methane over Ni-Al2O3 catalyst: possibility of CO2 conversion to hydrogen

The effect of CO2 feeding on syngas quality in autothermal reforming of methane over Ni-Al2O3 catalyst: possibility of CO2 conversion to hydrogen

Fisher–Tropsch Synthesis for Conversion of Methane into Liquid Hydrocarbons through Gas-to-Liquids (GTL) Process: A Review

The interest in Gas-to-Liquid technology (GTL) is growing worldwide because it involves a two-step indirect conversion of natural gas to higher hydrocarbons ranging from Liquefied Petroleum Gas (LPG) to paraffin wax. GTL makes it possible to obtain clean diesel, naphtha, lubes, olefins, and other industrially important organics from natural gas. This article is a brief review discussing the state-of-the-art of GTL, including the basics of syngas manufacturing as a source for Fischer-Tropsch synthesis (FTS), hydrocarbons synthesis (Fischer-Tropsch process), and product upgrading. Each one is analyzed, and the main characteristics of traditional and catalysts technologies are presented. For syngas generation, steam methane reforming, partial oxidation, two-step reforming, and autothermal reforming of methane are discussed. For Fischer–Tropsch, we highlight the role of catalysis and selectivity to high molecular weight hydrocarbons. Also, new reactors technologies, such as microreactors, are presented. The GTL technology still faces several challenges; the biggest is obtaining the right H2:CO ratio when using a low steam-to-carbon ratio. Despite the great understanding of the carbon formation mechanism, little has been made in developing newer catalysts. Since 60–70% of a GTL plant cost is for syngas production, it needs more attention, particularly for developing the catalytic partial oxidation process (CPO), given that modern CPO processes using a ceramic membrane reactor reduce the plant’s capital cost. Improving the membrane’s mechanical, thermal, and chemical stability can commercialize the process. Catalytic challenges accompanying the FTS need attention to enhance the selectivity to produce high-octane gasoline, lower the production cost, develop new reactor systems, and enhance the selectivity to produce high molecular weight hydrocarbons. Catalytically, more attention should be given to the generation of a convenient catalyst layer and the coating process for a given configuration.

Optimization of the reaction conditions of steam/carbon dioxide and autothermal reforming of methane

Optimization of the reaction conditions of steam/carbon dioxide and autothermal reforming of methane

Optimization of the Reaction Conditions of Steam/Carbon Dioxide and Autothermal Reforming of Methane

Optimization of the Reaction Conditions of Steam/Carbon Dioxide and Autothermal Reforming of Methane

The effects of CO2/CH4 ratio on soot formation for autothermal reforming of methane at elevated pressure

Autothermal reforming of methane (ATR) technique is a promising technology for H2 production. Soot formed in the combustion region of ATR may deactivate the downstream catalyst used to enhance the reforming reactions. In this work, the effects of CO2/CH4 ratio on soot production and main gas-phase components involved in reforming reactions were investigated by experiment and numerical simulations in laminar inverse coflow diffusion flames, at conditions close to ATR. The CO2/CH4 ratio ranges from 0.27 to 4.90, and the pressure ranges from 1 atm to 10 atm. The oxidant consists 70% O2 and 30% N2 to mimic the oxy-combustion in the ATR process. The soot, polycyclic aromatic hydrocarbon (PAHs), OH* distribution, and flame structure were measured using planar laser-induced incandesce, planar laser-induced fluorescence, OH* luminescence, and flame luminescence, respectively. High fidelity simulations with a reduced gas-phase kinetic mechanism and soot aerosol models were also undertaken to supplement the findings. The results show that soot formation is suppressed by a higher CO2/CH4 ratio, while the level of soot reduction is attenuated as the pressure increases. The peak soot volume fraction increases with the flame height, and then levels off. PAHs concentration monotonically increases with flame height. The spatial distributions of PAH and soot along flame height were not well captured by numerical simulations, and the used physical based soot inception model is expected to account for the discrepancy. The peak soot volume fraction correlates with CO2/CH4 ratio by an exponentially decaying function, with the exponent decreasing with increasing pressure. A similar trend of PAHs concentration along with CO2/CH4 ratio was also observed. Non-sooting flame is achievable at elevated pressure if the CO2/CH4 ratio is higher than 4.0, at the expense of lowering the syngas yield in the combustion region. The simulations also predicted that the flame temperature and concentration of H2 and CO decrease with CO2/CH4 ratio.

Oxygen feeding strategies for methane ATR

The performance of different reactor designs for methane autothermal reforming (ATR) with diverse options of O 2 feeding is comparatively explored. The designs under consideration include a single bed reactor with O 2 feed at the inlet, multibed reactors in series with inter-bed oxygen injection, and a multitubular membrane reactor with O 2 feeding through the porous wall. The distribution of O 2 leads to low O 2 concentrations in the reaction mixture and less severe thermal conditions. The evolution of methane reforming and combustion reactions proceeds in parallel due to a suitable degree of reduction of the Ni catalyst. Particularly, the membrane reactor can produce H 2 in a more distributed way along the reactor. The leakage of O 2 at the membrane reactor outlet can be prevented with a final section of a non-porous wall. The modified membrane reactor demonstrates flexibility to carry out the methane ATR with lower temperatures without deterioration of H 2 yield. • The distribution of O 2 feeding leads to less severe thermal conditions. • Low O 2 concentrations allow a suitable degree of reduction of the catalyst. • The leakage of O 2 at the outlet of the membrane reactor is a drawback. • A final section of non-porous wall in the membrane reactor prevents the O 2 leakage. • Membrane reactor can perform methane ATR at lower temperatures with high yields of H 2 .

Syngas production via auto-thermal methane reforming using modified perovskite catalysts: Performance evaluation of La1−xGdxNiO3-δ perovskite oxides

A series of Gadolinium (Gd) substituted LaNiO3 nano catalyst specified as La1−xGdxNiO3-δ (x = 0, 0.3, 0.5, 0.7, 0.9 and 1) were synthesized by the modified citrate sol-gel method and applied in auto-thermal reforming of methane (ATR). The results of characterization techniques indicated all samples have a highly homogeneous and crystalline structure with particle sizes in the range of nano meters. X-Ray diffraction (XRD) patterns confirmed a pure crystallinity perovskite phase without the presence of any other crystalline phases for the samples with low Gd content (x = 0, 0.1). The formation of spinel (La2NiO4) and oxide (NiO, Gd2O3) phases could be increased by degree of substitution (x). Brunauer–Emmett–Teller (BET) results showed that the presence of Gd in the catalyst structure increases the specific surface area of the samples. Temperature programmed reduction (TPR) analysis showed difficult reduction pattern by enhancing the degree of substitution (x). Partial substitution of La by Gd was investigated in ATR process under reaction temperature range of 600 to 800 °C. All catalysts represented a high catalytic activity and stability toward syngas production via ATR process at 800 °C while at lower temperatures, the La1−xGdxNiO3-δ (x = 0, 0.1, 0.9 and 1) showed the highest activity.

Promoters for Improvement of the Catalyst Performance in Methane Valorization Processes

In this work, the introduction of modifying additives in the composition of catalysts is considered as an effective mode of improving functional characteristics of materials for two processes of methane conversion into valuable products – methane dehydroaromatization (DHA of CH4) into benzene and hydrogen and autothermal reforming of methane (ATR of CH4) into synthesis gas. The effect of type and content of promoters on the structural and electronic state of the active component as well as catalyst activity and stability against deactivation is discussed. For DHA of CH4 the operation mode of additives M = Ag, Ni, Fe in the composition of Mo-M/ZSM-5 catalysts was elucidated and correlated with the product yield and coke content. It was shown that when Ag serves as a promoter, the duration of the catalyst stable operation is enhanced due to a decrease in the rate of the coke formation. In the case of Ni and Fe additives, the Ni-Мо and Fe-Mo alloys are formed that retain the catalytic activity for a long time in spite of the carbon accumulation. For ATR of CH4, the influence of M = Pd, Pt, Re, Mo, Sn in the composition of Ni-M catalysts supported on La2O3 or Ce0.5Zr0.5O2/Al2O3 was elucidated. It was demonstrated that for Ni-M/La2O3 catalysts, Pd is a more efficient promoter that improves the reducibility of Ni cations and increases the content of active Nio centers. In the case of Ni-M/Ce0.5Zr0.5O2/Al2O3 samples, Re is considered the best promoter due to the formation of an alloy with anti-coking and anti-sintering properties. The use of catalysts with optimal promoter type and its content provides high efficiency of methane valorization processes.

Autothermal reforming of methane over an integrated solid oxide fuel cell reactor for power and syngas co-generation

Autothermal reforming of methane couples exothermal partial oxidation of methane and endothermal steam or dry reforming of methane to achieve high energy efficiency, which can be operated through solid oxide fuel cells (SOFCs) so that expensive oxygen is not required and safety issue caused by CH4/O2 mixture is avoided. In addition, electric power is simultaneously generated. This study has demonstrated the efficient electrochemical autothermal reforming of methane over a SOFC reactor integrated with catalyst beds within anode channel structure. The catalyst bed reformer increases syngas yield by a factor of about 6 owing to the increased methane conversion and syngas selectivity. By numerical assessment, enhanced mass transportation is well validated by high fuel accessibility at the electrode-electrolyte interface benefiting from the integrated catalyst beds. Compared with conventional catalyst layer on anode surface, the catalyst beds are more efficient for conducting methane reforming. After the initial stabilization of cell microstructure, the SOFC reactor has demonstrated stable cell performance and syngas yield during the test for 120 h. The integrated SOFC reactor has demonstrated a promising application in performing catalytic reforming reactions.

Hydrogen production from methane autothermal reforming over CaTiO3, BaTiO3 and SrTiO3 supported nickel catalysts

Nickel supported on perovskite supports were investigated in the autothermal reforming of methane. The catalysts were prepared by incipient wetness impregnation and characterized by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), N2 physisorption, H2 temperature programmed reduction (H2-TPR), H2 chemisorption, dehydrogenation of cyclohexane model reaction and Raman spectroscopy. The alumina supported catalyst exhibited highest initial conversion and selectivity to H2, however it deactivated. All catalysts with perovskite support were very stable, with Ni/CaTiO3 and Ni/BaTiO3 converting over 70% of the methane. Due to carbon formation, Ni/SrTiO3 conversion was only 50%. Turnover frequency was higher on perovskite supported catalysts. Deactivated Ni/Al2O3 favored total oxidation of methane instead of methane reforming, however the selectivity of catalysts supported on perovskites remained stable.

Thermodynamic analysis of autothermal steam‐reforming of methane for ammonia production

Autothermal reforming of methane is one of the most widely reported techniques for syngas production. This thermodynamic analysis discusses two aspects of autothermal reforming: first, to obtain hydrogen to nitrogen in the ratio 3:1, which is the most suitable feed ratio for ammonia production in the Haber–Bosch process, and then to find out the thermoneutral point of the process. Throughout the study, all simulations are carried out at 1 bar pressure and within the temperature range 500–1000°C. Conditions with more than 99% methane conversion and 0.1% coke deposition are considered. Other parameters taken into account for optimization are OMR (oxygen to methane ratio) in range 0.4–0.6, SMR (steam to methane ratio) in range 1.5–3.5 and oxygen enrichment in air from 25% to 40%. This study briefly discusses the water gas shift (WGS) reaction for CO removal and its conversion to H2. The best thermoneutral point for the reformer was found to be at OMR = 0.59845, SMR = 2.105, with an oxygen enrichment level of 39.4%.

Mechanism of the autothermal reforming reaction of methane on Pt(1 1 1) surfaces: A density functional theory study

Density functional theory calculations were carried out to better understand the reaction mechanism for the autothermal reforming of methane on Pt(1 1 1) surfaces. Particular focus was placed upon gaining a more complete understanding of the adsorption, oxidation, combination, and dehydrogenation processes involved in the autothermal reforming reaction. The adsorption energies for various species on the (1 1 1) surface were computed, and the preferred adsorption geometry for various species was determined. The primary reaction pathways were determined based on the reaction barriers and energies for all the elementary steps involved in the processes. The results indicated that the preferred adsorption oxygen-containing species is formyl due to its lowest adsorption energy on the (1 1 1) surface. Methane can be dissociated on the (1 1 1) surface to generate methyl and then further oxidatively dehydrogenated to form carbon. The elementary reaction pathways involving hydroxyl radicals play a minor role in the overall autothermal reforming process due to the low coverage of hydroxyl radicals on the (1 1 1) surface. The reaction pathways involving hydroxyl radicals may be relevant only to the formation process of methanol fragments from carbon adsorbed on the (1 1 1) surface due to its low reaction barrier. Finally, the primary reaction pathways are the oxidation of methane on the (1 1 1) surface: CH4 → CH3,adsorbed → CH2,adsorbed → CHadsorbed → Cadsorbed → COadsorbed.

Hydrogen production through autothermal reforming of CH4: Efficiency and action mode of noble (M = Pt, Pd) and non-noble (M = Re, Mo, Sn) metal additives in the composition of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts

Hydrogen production through autothermal reforming of methane (ATR of CH4) over promoted Ni catalysts was studied. The control of the ability to self-activation and activity of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts was achieved by tuning their reducibility through the application of different types (M = Pt, Pd, Re, Mo or Sn) and content (molar ratio M/Ni = 0.003, 0.01 or 0.03) of additive. The comparison of the efficiency and action mode of noble (M = Pt, Pd) and non-noble (M = Re, Mo, Sn) metal additives in the composition of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts was performed using X-ray fluorescence analysis, N2 adsorption, X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction with hydrogen, and thermal analysis. The composition-characteristics-activity correlations were determined. It was shown that the introduction of a promoter does not affect the textural and structural properties of catalysts but influences their reducibility and performance in ATR of CH4. At the similar dispersion of NiO active component (11 ± 2 nm), the Ni2+ reduction is intensified in the following order of additives: Mo < Sn < Re ≤ Pd < Pt. It was found that for the activation of Ni and Ni–Sn catalysts before ATR of CH4 tests, the pre-reduction is required. On the contrary, the introduction of Pt, Pd and Re additives leads to the self-activation of catalysts under the reaction conditions and an increase of the H2 yield due to the enhanced reducibility of Ni2+. The efficient and stable catalyst for hydrogen production has been developed: in ATR of CH4 at 850 °C over an optimum 10Ni-0.9Re/Ce0.5Zr0.5O2/Al2O3 catalyst the H2 yield of 70% is attained. The designed catalyst has enhanced stability against oxidation and sintering of Ni active component as well as high resistance to coking.

Numerical simulation of heat‐pipe and folded reformers for efficient hydrogen production through methane autothermal reforming

In order to intensify the methane autothermal reforming (ATR) process for efficient hydrogen production, novel heat-pipe and the folded reactors were designed and studied by numerical simulations. The reactor performance, such as methane conversion rate, hydrogen yield, and temperature difference between the reactor inlet and outlet, was computed and compared for both traditional tubular reactors and the novel reactors. Under the optimum operating parameters, compared with the tubular reactor, the heat pipe reactor and the folded reactor can help to increase methane conversion rate from 34% to 45% and 50%, while hydrogen productivity from 22.2% to 28.6% and 31.4%, respectively. The performance of the heat pipe reactor depends on the length and position of the heat pipe, while for the folded reactor, thicker intermediate plate with higher thermal conductivity material is more beneficial. Results were compared with previous experiments and could be used as a reference to guide new experimental and theoretical works toward the ultimate goal of designing and optimizing the ATR reactors for hydrogen production in the future.

Steam, dry and autothermal methane reforming for hydrogen production: A thermodynamic equilibrium analysis

Environmental issues of fossil fuels use in energy systems are boosting research in the field of H2 generation. Although steam reforming is the most well-established process for H2 production, alternative thermochemical routes are emerging.The paper aims to compare three reforming processes: steam methane reforming, dry methane reforming and autothermal methane reforming. To this end, a thermodynamic equilibrium model is developed and validated via comparison with literature data. The influence of operating conditions on the performance of the reforming options is investigated, addressing chemical and energy-related aspects. Regarding the former, attention is focused on H2 yield and selectivity over CO and CO2. From the energy viewpoint, performance indices investigated include the lower heating value of syngas, the reformer thermal power requirement and the chemical energy increase of fuel at the reformer exit. An H2 production efficiency is also evaluated to directly compare steam, dry and autothermal methane reforming.The study revealed that moderate pressures and oxidant-to-methane ratios allow finding the best compromise between H2 production and process efficiency in all investigated reforming options; under these conditions, steam methane reforming performs better than dry methane reforming; however, when the reformer operates under autothermal conditions, the performance of dry methane reforming approaches that of steam methane reforming.

Spectroscopic and kinetic insights into the methane reforming over Ce-pyrochlores

High thermal stability and oxygen conductivity of pyrochlores makes them a potential catalyst for the dry reforming of methane (DRM). In this study, noble metal (Pt, Ru) substituted Ce2Zr2O7 and Ce2Ti2O7 pyrochlores have been synthesized by modified Pechini method. The effect of variation of dopant concentration and position was examined to achieve strong metal-support interaction. Ce2Zr1.96Pt0.04O7-δ exhibited the best catalytic activity towards DRM and hence, been studied for partial oxidation (POM) and autothermal reforming of methane (ATR). Syngas ratio (H2/CO) was tuned by varying the O2 concentration in the feed. Insights obtained from both ex-situ and in situ characterization were exploited to discern the reaction mechanism. The surface intermediates were examined by DRIFTS on Ce2Zr1.96Pt0.04O7-δ for DRM, POM and ATR. Besides adsorbed CH4 and CO on Pt, the presence of carbonate and formate species were also identified. Thus, a dual-site mechanism via carbonate and formate formation was proposed for DRM over Ce2Zr1.96Pt0.04O7-δ.