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Kinetic studies of methanol dehydrogenation. Part I: copper-silica catalysts

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Abstract

A series of Cu/SiO2 catalysts was prepared using incipient wetness impregnation of silica gel with an aqueous solution of copper nitrate. The copper loading was 5 wt%. After the calcination, the catalyst was reduced in a hydrogen flow at varied temperatures (200, 300, and 400 °C). A conventional fixed bed reactor system was used to study the kinetics of methanol dehydrogenation to methyl formate. Methyl formate decomposition to carbon monoxide and hydrogen was taken into account as a main side reaction. Observable rate constants were determined. The temperature of reductive pretreatment of the catalysts was shown to affect strongly their catalytic behavior in the studied reaction. The highest methyl formate yield was achieved for the sample reduced at 200 °C. An increase of reduction temperature up to 400 °C worsens the selectivity towards the main product in approximately by a factor of 2. The kinetic parameters obtained were used for modelling the process in a tubular reactor. Good agreement of theoretical and experimental data was found.

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Abbreviations

Ci :

Concentration of component i (kmol m−3)

cp :

Heat capacity (kJ g−1 K−1)

Dei :

Effective coefficient of radial diffusion of i-component (m2 s−1)

−∆Hj :

Heat effect of reaction j (kJ mol−1)

Keq :

Equilibrium constant

l:

Length of reactor (m)

N:

Number of components in a mixture

NR :

Number of reactions

P0 :

Pressure at normal conditions (atm)

R1 :

Radius of reactor (m)

r:

Radial coordinate in fixed bed catalyst (m)

R:

Universal gas constant (J mol−1 K−1)

S:

Selectivity (%)

T:

Temperature (K)

T0 :

Temperature at normal conditions (K)

Tw :

Temperature of the wall (K)

ul :

Axial velocity (m s−1)

wj :

Rate of reaction j (kmol kg −1cat  s−1)

X:

Conversion (%)

\(\text{Re}_{e}\) :

Reynolds number, \(\text{Re}_{e} = v_{e} d_{e} \rho_{g} /\mu\)

\(Sc\) :

Schmidt number (diffusion Prandtl’s criterion), \(Sc = \mu /(\rho_{g} D_{m} )\)

\(\Pr\) :

Prandtl number, \(\Pr = \mu \,c_{p} /\lambda_{g}\)

α:

Heat-transfer coefficient between the exterior wall of reactor and fixed bed catalyst (kJ m−2 s−1 K−1)

ε:

Porosity of the catalyst layer

γij :

Stoichiometric coefficient for component i in reaction j

λef :

Effective coefficient of radial thermal conductivity (J m−1 s−1 K−1)

τc :

Contact time (s)

ρG :

Density of the gas mixture (kg m−3)

ρk :

Density of the catalyst (kg m−3)

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Acknowledgements

This work was supported by Russian Foundation for Basic Research (grant number 16-38-00095).

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Authors and Affiliations

  1. Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, Russia, 630090

    Ekaterina V. Shelepova, Ludmila Yu Ilina & Aleksey A. Vedyagin

  2. National Research Tomsk Polytechnic University, Lenin av., 30, Tomsk, Russia, 634050

    Ekaterina V. Shelepova & Aleksey A. Vedyagin

Authors
  1. Ekaterina V. Shelepova
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  2. Ludmila Yu Ilina
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  3. Aleksey A. Vedyagin
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Correspondence to Aleksey A. Vedyagin.

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Shelepova, E.V., Ilina, L.Y. & Vedyagin, A.A. Kinetic studies of methanol dehydrogenation. Part I: copper-silica catalysts. Reac Kinet Mech Cat 120, 449–458 (2017). https://doi.org/10.1007/s11144-016-1135-1

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