Kinetic study of steam reforming of methanol over copper-based catalysts

Jiang, Chao; Trimm, D.L.; Wainwright, Mark; Cant, Noel W.

doi:10.1016/0926-860x(93)85197-w

Cited by 269 publications

(155 citation statements)

References 8 publications

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“…Regarding the reaction mechanism of methanol steam reforming over copper-based catalysts, four schemes have been proposed [7] including a methanol decomposition-water gas shift reaction scheme [71], a 1-step methanol steam reforming scheme [72,73], a methanol steam reforming-methanol decomposition-reverse water gas shift reaction scheme [74,75] and a methyl formate scheme [76][77][78]. The methanol steam reforming-methanol decomposition-reverse water gas shift reaction scheme is also adopted for methanol steam reforming over palladium catalysts [79,80].…”

Section: Reaction Mechanism Of Methanol Steam Reformingmentioning

confidence: 99%

Review on Copper and Palladium Based Catalysts for Methanol Steam Reforming to Produce Hydrogen

Shuai

2017

Catalysts

109

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Abstract:Methanol steam reforming is a promising technology for producing hydrogen for onboard fuel cell applications. The methanol conversion rate and the contents of hydrogen, carbon monoxide and carbon dioxide in the reformate, significantly depend on the reforming catalyst. Copper-based catalysts and palladium-based catalysts can effectively convert methanol into hydrogen and carbon dioxide. Copper and palladium-based catalysts with different formulations and compositions have been thoroughly investigated in the literature. This work summarized the development of the two groups of catalysts for methanol steam reforming. Interactions between the activity components and the supports as well as the effects of different promoters were discussed. Compositional and morphological characteristics, along with the methanol steam reforming performances of different Cu/ZnO and Pd/ZnO catalysts promoted by Al 2 O 3 , CeO 2 , ZrO 2 or other metal oxides, were reviewed and compared. Moreover, the reaction mechanism of methanol steam reforming over the copper based and palladium based catalysts were discussed.

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Section: Reaction Mechanism Of Methanol Steam Reformingmentioning

confidence: 99%

Review on Copper and Palladium Based Catalysts for Methanol Steam Reforming to Produce Hydrogen

Shuai

2017

Catalysts

109

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“…CO 2 + 3H 2 ) can be regarded as the reversed methanol synthesis reaction. However, a detailed reaction mechanism is still under debate (5,6,7). In a kinetic model by Peppley et al it is assumed that different active phases are responsible for the methanol decomposition, methanol-steam reforming, and the water-gas shift reaction (8).…”

Section: Introductionmentioning

confidence: 99%

Redox Behavior of Copper Oxide/Zinc Oxide Catalysts in the Steam Reforming of Methanol Studied by in Situ X-Ray Diffraction and Absorption Spectroscopy

Günter

Ressler

Jentoft

et al. 2001

Journal of Catalysis

249

162

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The bulk structure of copper in various binary Cu/ZnO catalysts for steam reforming of methanol under activation and working conditions is studied by in situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The evolution of bulk phases from CuO/ZnO precursors during activation with hydrogen was studied using temperature programmed reduction (TPR) (448 -523 K, 2 vol-% H 2 with and without water vapor). With decreasing copper content the onset of reduction is shifted from 473 K (pure CuO) to 443 K (40 mol-% Cu) accompanied by a decrease in Cu crystallite sizes (from 210 Å to 40 Å). Using time -resolved in situ XANES measurements at the Cu K edge during TPR experiments the degree of reduction was monitored. It is shown that Cu(I) oxide forms prior to Cu. Adding oxygen to the feed gas leads to the formation of a mixture of Cu(II) and Cu(I) oxide accompanied by a complete loss of activity. After switching back to steam reforming conditions a higher activity is attained while the catalyst shows an increased Cu crystallite size (up to 40%). EXAFS measurements at the Cu K and the Zn K edge indicate a structural disorder of the Cu particles in the medium range order based on increasing Debye-Waller factors for higher Cu-Cu shells . Furthermore, the dissolution of Zn atoms (up to ~ 4 mol-%) in the copper lattice is detected. Upon oxidation/reduction cycles activity is increased, the disorder in the copper particles increases, and Zn segregates out of the copper bulk. A structural model is proposed which ascribes the enhanced activity to structurally disordered (strained) copper particles due to an improved interface interaction with ZnO.

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“…Presently, a completely tuned and commonly used formulation in the industry is the CuO/ZnO/Al 2 O 3 catalyst [5,[10][11][12]. Improving this 03- catalyst in terms of selectivity and activity would have direct repercussion on the integration of low temperature methanol steam reforming (LT-MSR) and HT-PEMFC.…”

Section: Introductionmentioning

confidence: 99%

Low-temperature methanol steam reforming kinetics over a novel CuZrDyAl catalyst

Silva

Mateos-Pedrero

Ribeirinha

et al. 2015

Reac Kinet Mech Cat

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A kinetic study within the low-temperature methanol steam reforming (MSR) reaction range (170 ºC -200 ºC) was performed over a novel CuZrDyAl catalyst. The physicochemical and catalytic properties of the CuZrDyAl catalyst were compared with those of a conventional CuO/ZnO/Al 2 O 3 (G66 MR, Süd-Chemie) sample, taken as reference. The in-house catalyst displays better performances, in terms of methanol conversion and H 2 production, than the reference G66 MR sample.Interestingly, the in-house catalyst is significantly more selective (namely, yielding lower CO concentration) than the commercial one, which gives extra interest for producing fuel cell grade hydrogen. Physicochemical characterization evidences that the in-house catalyst have improved reducibility of copper species compared with the G66-MR, which might account for its better performances.The parameters of a simple power-law equation and two mechanistic kinetic models were determined by non-linear regression, minimizing the sum of the residual squares; the best fitting with the experimental data was obtained when using Model 3, based on the reported work from Peppley et al. [10] for the commercial CuO/ZnO/Al 2 O 3 .This article was published in Reaction Kinetics, Mechanisms and Catalysis, 115(1), 321-339, 2015 http://dx.doi.org/10.1007/s11144-015-0846-z 03-11-2017 2 Noteworthy, is the scarce number of MSR kinetic studies at such lower temperature range.

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Kinetic study of steam reforming of methanol over copper-based catalysts

Cited by 269 publications

References 8 publications

Review on Copper and Palladium Based Catalysts for Methanol Steam Reforming to Produce Hydrogen

Review on Copper and Palladium Based Catalysts for Methanol Steam Reforming to Produce Hydrogen

Redox Behavior of Copper Oxide/Zinc Oxide Catalysts in the Steam Reforming of Methanol Studied by in Situ X-Ray Diffraction and Absorption Spectroscopy

Low-temperature methanol steam reforming kinetics over a novel CuZrDyAl catalyst

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