Production of hydrogen from methanol over binary Cu/ZnO catalysts

Agrell, Johan; Boutonnet, Magali; Melián‐Cabrera, Ignacio; Fierro, J.L.G.

doi:10.1016/s0926-860x(03)00520-9

Cited by 158 publications

(154 citation statements)

References 45 publications

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“…The evolution of products stems from exposing the oxidized catalyst to methane. The CO 2 and H 2 O were formed first, then CO and H 2 were detected for the switch reaction over the fully oxidized LaFeO 3 catalyst. But the intensity of CO 2 did not decline immediately when the CO began to be detected.…”

Section: Resultsmentioning

confidence: 97%

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst

Dai

et al. 2006

J. Phys. Chem. B

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A redox cycle process, in which CH 4 and air are periodically brought into contact with a solid oxide packed in a fixed-bed reactor, combined with the water-gas shift (WGS) reaction, is proposed for hydrogen production. The sole oxidant for partial oxidation of methane (POM) is found to be lattice oxygen instead of gaseous oxygen. A perovskite-type LaFeO 3 oxide was prepared by a sol-gel method and employed as an oxygen storage material in this process. The results indicate that, under appropriate reaction conditions, methane can be oxidized to CO and H 2 by the lattice oxygen of LaFeO 3 perovskite oxide with a selectivity higher than 95% and the consumed lattice oxygen can be replenished in a reoxidation procedure by a redox operation. It is suggested that the POM to H 2 /CO by using the lattice oxygen of the oxygen storage materials instead of gaseous oxygen should be possibly applicable. The LaFeO 3 perovskite oxide maintained relatively high catalytic activity and structural stability, while the carbonaceous deposits, which come from the dissociation of CH 4 in the pulse reaction, occurred due to the low migration rate of lattice oxygen from the bulk toward the surface. A new dissociation-oxidation mechanism for this POM without gaseous oxygen is proposed based on the transient responses of the products checked at different surface states via both pulse reaction and switch reaction over the LaFeO 3 catalyst. In the absence of gaseous-phase oxygen, the rate-determining step of methane conversion is the migration rate of lattice oxygen, but the process can be carried out in optimized cycles. The product distribution for POM over LaFeO 3 catalyst in the absence of gaseous oxygen was determined by the concentration of surface oxygen, which is relevant with the migration rate of lattice oxygen from the bulk toward the surface. This process of hydrogen production via selective oxidation of methane by lattice oxygen is better in avoiding the deep oxidation (to CO 2 ) and enhancing the selectivity. Therefore, this new route is superior to general POM in stability (resistance to carbonaceous deposition), safety (effectively avoiding accidental explosion), ease of operation and optimization, and low cost (making use of air not oxygen).

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Section: Resultsmentioning

confidence: 97%

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst

Dai

et al. 2006

J. Phys. Chem. B

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“…Reduction peak for similar catalysts was placed between 180-240°C and reducibility decreased after reoxidation to temperatures ranging from 220 to 250°C. High temperature reduction maxima were explained by strong interaction between ZnO and CuO [14]. High temperature peaks on the TPR curves of Cu/ZnO catalysts have been also ascribed to the reduction of ZnO in the vicinity of copper metallic species.…”

Section: Cuo-zno-1mentioning

confidence: 91%

An Application of Microemulsion Method for Synthesis of Copper-Zinc Materials

Pawlonka¹,

Słowik²,

Gac³

et al. 2014

Annales UMCS, Chemia

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Microemulsion method was used for preparation of copperzinc mixed oxides. Samples were prepared from the solutions containing zinc and copper nitrates. Sodium carbonate was used as a precipitant and hydrazine as reducing agent. Water-in-oil (W/O) microemulsions were formed by the application of cyclohexane, isopropyl alcohol, and hexadecyltrimethylammonium bromide (CTAB) as surfactant. The aim of the studies was determination of the influence of the sequence of synthesis stages on the formation of materials, their surface and structural properties. Thermal decomposition studies of materials were carried out by infrared spectroscopy. The physicochemical properties were characterized by nitrogen adsorption-desorption method, X-ray diffraction (XRD) and temperature-programmed reduction (TPR).

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“…TPR (temperature programmed reduc tion) experiments comparing Cu/ZnO with ZrO2 and/or Al2O3-incorporated Cu/ZnO catalysts showed that ZrO2 and/or Al2O3 doping retarded Cu/CuO particle growth in successive TPR/TPO (temperature programmed oxi dation) measurements 17) . Incorporation of ZrO2 into the Cu/ZnO catalyst may stabilize the dispersed copper on the support, ensuring that the Cu surface area is rela tively stable during the reaction.…”

Section: Cu Dispersion and Stabilitymentioning

confidence: 99%

Steam Reforming of Dimethyl Ether over Cu/ZnO/ZrO2 and γ-Al2O3 Mixed Catalyst Prepared by Extrusion

博之¹,

渉²,

知哉³

et al. 2008

J. Jpn. Petrol. Inst.

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Steam reforming of dimethyl ether, DME, over Cu/ZnO/ZrO2 and γ-Al2O3 mixed catalysts prepared by the extrusion technique was investigated. The catalysts were characterized by BET, pore-size distribution measure ments, N2O chemisorption, powder X-ray diffraction, and SEM-EDX analysis. The effect of reaction tempera ture on catalyst life time was investigated. Steam reforming of DME over the extruded catalyst proceeded above 623 K. The major reaction products were H2 and CO2 with relatively small amounts of CO and CH4. DME steam reforming was not restricted by the equilibrium limitation of DME hydration to CH3OH, suggesting that CH3OH produced was subsequently reformed into H2 and CO2 over the catalyst. The catalyst suffered from thermal deactivation at higher temperatures; mainly caused by a reduction in Cu dispersion in the Cu/ZnO/ZrO2 catalyst. Incorporation of ZrO2 into Cu/ZnO may stabilize Cu dispersion and increase the stability of the extruded catalyst for long-term operation.

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Production of hydrogen from methanol over binary Cu/ZnO catalysts

Cited by 158 publications

References 45 publications

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst

An Application of Microemulsion Method for Synthesis of Copper-Zinc Materials

Steam Reforming of Dimethyl Ether over Cu/ZnO/ZrO<sub>2</sub> and γ-Al<sub>2</sub>O<sub>3</sub> Mixed Catalyst Prepared by Extrusion

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Production of hydrogen from methanol over binary Cu/ZnO catalysts

Cited by 158 publications

References 45 publications

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO3Perovskite Catalyst

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO3Perovskite Catalyst

An Application of Microemulsion Method for Synthesis of Copper-Zinc Materials

Steam Reforming of Dimethyl Ether over Cu/ZnO/ZrO<sub>2</sub> and γ-Al<sub>2</sub>O<sub>3</sub> Mixed Catalyst Prepared by Extrusion

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Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst

Hydrogen Production from a Combination of the Water−Gas Shift and Redox Cycle Process of Methane Partial Oxidation via Lattice Oxygen over LaFeO₃Perovskite Catalyst