Optimization of the methanol oxidation over iron–molybdate catalysts

Ivanov, K.; Dimitrov, D.; Boyanov, B.

doi:10.1016/j.cej.2009.04.049

Cited by 17 publications

(12 citation statements)

References 9 publications

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“…6. Our experience has shown that the pure copper oxide has a low activity toward the oxidation of DME [20], which is confirmed by the results in Fig. 6.…”

Section: Resultssupporting

confidence: 93%

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Mechanochemical Synthesis and Characterization of Nanocrystalline Copper–Cobalt Ferrites

Velinov

Dimitrov²,

Koleva

et al. 2015

Acta Metall. Sin. (Engl. Lett.)

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Nanocrystalline copper-cobalt ferrites with composition Cu 1-x Co x Fe 2 O 4 , where x = 0.2 and 0.8, were synthesized by mechanochemical treatment of co-precipitated precursors. The ferrite powders were characterized by XRD and Mössbauer spectroscopy. Results proved obtaining of spinel ferrites with crystallite size smaller than 10 nm. Increasing of crystallite size of samples with increasing of mechanochemical treatment duration was established, too. Catalytic properties of obtained ferrites were tested in reactions of oxidation of CO, methanol and dimethyl ether. High catalytic activity of nanocrystalline copper-cobalt ferrites toward CO and CH 3 OH (about 100% conversions of CO and CH 3 OH at 160°C) and moderate activity toward (CH 3 ) 2 O oxidation were established. The results obtained revealed that the Co/Cu atomic ratio is an important factor determinant the behavior of catalysts toward methanol and DME oxidation.

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“…6. Our experience has shown that the pure copper oxide has a low activity toward the oxidation of DME [20], which is confirmed by the results in Fig. 6.…”

Section: Resultssupporting

confidence: 93%

“…4. The activity of the mixed catalyst significantly exceeds that of the pure CuO under the same conditions of conducting the CO oxidation [20].…”

Section: Resultsmentioning

confidence: 99%

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Mechanochemical Synthesis and Characterization of Nanocrystalline Copper–Cobalt Ferrites

Velinov

Dimitrov²,

Koleva

et al. 2015

Acta Metall. Sin. (Engl. Lett.)

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“…As mentioned previously, the constraints of process safety which require the operation of this highly exothermic process in multitubular reactors below the explosion limit of the air–methanol mixture lead to low‐specific productivity and restrict the production capacity . Gribovskii et al have stated that the technological constraints of the kinetic characteristics of the Fe‐Mo process have not allowed improvement in intensification despite efforts in increasing catalyst activity, increasing inlet methanol concentration, increasing mixture heat capacity, and changing reactor configuration . The low production rate also implies a low gas flow rate which negatively impacts the heat and mass transfer rates in the bed and encourages nonuniformity of temperature and concentration .…”

Section: Introductionmentioning

confidence: 99%

“…24 Gribovskii et al have stated that the technological constraints of the kinetic characteristics of the Fe-Mo process have not allowed improvement in intensification 23 despite efforts in increasing catalyst activity, 25 increasing inlet methanol concentration, 24 increasing mixture heat capacity, 26 and changing reactor configuration. 27 The low production rate also implies a low gas flow rate which negatively impacts the heat and mass transfer rates in the bed and encourages nonuniformity of temperature and concentration. 24 On the other hand, Andersson et al 3 have enumerated process-related factors which have led to increases in productivity, such as gas recirculation, the use of pre-calcined catalyst rings to replace granules and obtain lower pressure drop and higher flow rates, pressurization and in the FORMOX process the development of refined catalyst activity profiles, which improve the reaction rate and temperature profile along the reactor tube by introducing several layers of catalyst particles along the tube (e.g., inert particles, mixed particles).…”

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confidence: 99%

Effect of particle shape on methanol partial oxidation in a fixed bed using CFD reactor modeling

Partopour

Dixon

2020

AIChE Journal

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Particle shape is one of the most important parameters in the design and optimization of fixed‐bed processes. To address the impact of particle shape on methanol partial oxidation to formaldehyde over molybdate catalyst, packings of spheres, cylinders, rings, and trilobes are numerically generated. The generated packings are used to carry out resolved particle Computational Fluid Dynamics (CFD) simulations under industrial conditions. Pressure drop, voidage and velocity profiles, radial heat transfer, and local and overall conversion and selectivity results are presented. Despite their lower particle surface area, lower particle effectiveness and more uneven flow distribution than trilobes, and lower overall heat transfer coefficient than cylinders, rings had the best conversion and selectivity due to their balance between the factors. Three longer tubes of rings, rings and cylinders, and rings and trilobes are simulated and show a small gain in selectivity for the rings and trilobes.

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Reaction Mechanism of Methanol to Formaldehyde over Fe‐ and FeO‐Modified Graphene

et al. 2015

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We employed periodic DFT calculations (PBE-D2) to investigate the catalytic conversion of methanol over graphene embedded with Fe and FeO. Two possible pathways of dehydrogenation to formaldehyde and dehydration to dimethyl ether (DME) over these catalysts were examined. Both processes are initiated with the activation of methanol over the catalytic center through O-H cleavage. As a result, a methoxo-containing intermediate is formed. Subsequently, H-transfer from the methoxy to the adjacent ligand leads to the formation of formaldehyde. Conversely, the activation of the second methanol over the intermediate gives DME and H2O. Over Fe/graphene, the dehydration process is kinetically and thermodynamically preferable. Unlike Fe/graphene, FeO/graphene is predicted to be an efficient catalyst for the dehydrogenation process. Oxidative dehydrogenation over FeO/graphene takes place through two steps with free energy barriers of 5.7 and 10.2 kcal mol(-1).

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Optimization of the methanol oxidation over iron–molybdate catalysts

Cited by 17 publications

References 9 publications

Mechanochemical Synthesis and Characterization of Nanocrystalline Copper–Cobalt Ferrites

Mechanochemical Synthesis and Characterization of Nanocrystalline Copper–Cobalt Ferrites

Effect of particle shape on methanol partial oxidation in a fixed bed using CFD reactor modeling

Reaction Mechanism of Methanol to Formaldehyde over Fe‐ and FeO‐Modified Graphene

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