Partial oxidation of methane over the perovskite oxides

Ba0.5Sr0.5Co0.8Fe0.2O3-delta and Ba0.5Sr0.5Co0.8Ti0.2O3-delta oxides were synthesized by a combined EDTA-citrate complexing method. The catalytic behavior of these two oxides with the perovskite structure was studied during the reaction of methane oxidation. The pre-treatment with methane has different effect on the catalytic activities of both the oxides. The methane pre-treatment has not resulted in the change of the catalytic activity of BSCFO owing to its excellent reversibility of the perovskite structure resulting from the excellent synergistic interaction between Co and Fe in the oxide. However, the substitution with Ti on Fe-site in the lattice makes the methane pre-treatment have an obvious influence on the activity of the formed BSCTO oxide.

Improved Efficiency for Partial Oxidation of Methane by Controlled Copper Deposition on Surface-Modified ZSM-5

The mono(μ-oxo) dicopper cores present in the pores of Cu-ZSM-5 are active for the partial oxidation of methane to methanol. However, copper on the external surface reduces the ratio of active, selective sites to unselective sites. More efficient catalysts are obtained by controlling the copper deposition during synthesis. Herein, the external exchange sites of ZSM-5 samples were passivated by bis(trimethylsilyl) trifluoroacetamide (BSTFA) followed by calcination, promoting selective deposition of intraporous copper during aqueous copper ion exchange. At an optimum level of 1–2 wt % SiO2, IR studies showed a 64 % relative reduction in external copper species and temperature-programmed oxidation analysis showed an associated increase in the formation of methanol compared with unmodified Cu-ZSM-5 samples. It is, therefore, reported that the modified zeolites contained a significantly higher proportion of active, selective copper species than their unmodified counterparts with activity for partial methane oxidation to methanol.

The partial oxidation of methane over Pd/Al2O3 catalyst nanoparticles studied in-situ by near ambient-pressure x-ray photoelectron spectroscopy

Near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is used to study the chemical state of methane oxidation catalysts in-situ. Al2O3{supported Pd catalysts are prepared with different particle sizes ranging from 4 nm to 10 nm. These catalysts were exposed to conditions similar to those used in the partial oxidation of methane (POM) to syn-gas and simultaneously monitored by NAP-XPS and mass spectrometry. NAP-XPS data show changes in the oxidation state of the palladium as the temperature in- creases, from metallic Pd0 to PdO, and back to Pd0. Mass spectrometry shows an increase in CO production whilst the Pd is in the oxide phase, and the metal is reduced back under presence of newly formed H2. A particle size effect is observed, such that CH4 conversion starts at lower temperatures with larger sized particles from 6 nm to 10 nm. We find that all nanoparticles begin CH4 conversion at lower temperatures than polycrystalline Pd foil.

Partial oxidation of methane on NiO-MgO-ZrO2 catalysts

Catalysts containing mixtures of NiO, MgO and ZrO2 were synthesized by the polymerization method. They were characterized by X-ray diffraction (XRD), physisorption of N-2 (BET), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES), and then tested in the partial oxidation of methane (POM) in the presence of air (2CH(4):1O(2)) at 750 degrees C for 6 h. Among the ternary oxides, the catalyst with 40 mol% MgO showed the highest conversion rates in the catalytic processes, but also the highest carbon deposition values (48 mmol h (1)). The greater the amount of NiO-MgO solid solution formed, the higher was the conversion rate of reactants (CH4), peaking at 40 mol% of MgO. Catalysts with lower Ni content on the surface achieved a high rate of CH4 conversion into synthesis gas (H-2 + CO). The formation of more NiO-MgO solid solution seemed to inhibit the deactivation of Ni degrees during reaction. The values of the H-2/CO product ratio were generally found to be slightly lower than stoichiometric. (C) 2012 Elsevier Ltd. All rights reserved.

Direct synthesis of methanol by partial oxidation of methane with oxygen over cobalt modified mesoporous H-ZSM-5 catalyst

Peer reviewed