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Simultaneous hydrogen and methanol enhancement through a recuperative two-zone thermally coupled membrane reactor

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Abstract

In this work, a novel configuration with two zones instead of one single integrated catalytic bed in thermally coupled membrane reactor (TCMR) is developed for enhancement of simultaneous methanol, benzene and hydrogen production. In the first zone, the synthesis gas is partly converted to methanol in a conventional water-cooled reactor. In the second zone, the reaction heat is used to drive the endothermic dehydrogenation of cyclohexane reaction in second tube side. Selective permeation of hydrogen through the Pd–Ag membrane is achieved by co-current flow of sweep gas through the permeation side. The length of first zone is chosen equal 35 cm which the optimization procedure obtained this value. The proposed model has been used to compare the performance of a two-zone thermally coupled membrane reactor (TZTCMR) with conventional reactor (CR) and TCMR at identical process conditions. The simulation results represent 13.14 % enhancement in the production of pure hydrogen in comparison with TCMR. Moreover, 2.96 and 4.54 % enhancement of the methanol productivity relative to TCMR and CR were seen, respectively, owing to utilizing higher temperature at the first parts of reactor for higher reaction rate and then reducing temperature gradually at the end parts of reactor for increasing thermodynamics equilibrium conversion in TZTCMR.

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Abbreviations

\(a_{v}\) :

Specific surface area of catalyst pellet (m\(^{2}\) m\(^{-3}\))

\(A_{c}\) :

Cross section area of each tube (m\(^{2}\))

\(A_{i}\) :

Inside area of inner tube (m\(^{2}\))

\(A_{o}\) :

Outside area of inner tube (m\(^{2}\))

\(A_{s}\) :

lateral area of each tube (m\(^{2}\))

\(C\) :

Total concentration (mol m\(^{-3}\))

\(C_{p}\) :

Specific heat of the gas at constant pressure (J mol\(^{-1}\))

\(d_{p}\) :

Particle diameter (m)

\(D_{i}\) :

Tube inside diameter (m)

\(D_{ij}\) :

Binary diffusion coefficient of component \(i\) in \(j\) (m\(^{2}\) s\(^{-1}\))

\(D_{im}\) :

Diffusion coefficient of component \(i\) in the mixture (m\(^{2}\) s\(^{-1}\))

\(D_{o}\) :

Tube outside diameter (m)

\(D_{sh}\) :

Shell inside diameter (m)

\(f_{i}\) :

Partial fugacity of component \(i\) (bar)

\(F\) :

Total molar flow rate (mol s\(^{-1}\))

\(G\) :

Mass velocity (kg m\(^{-2}\) s\(^{-1}\))

\(h_{f}\) :

Gas-solid heat transfer coefficient (W m\(^{-2}\) K\(^{-1}\))

\(h_{i}\) :

Heat transfer coefficient between fluid phase and reactor wall in exothermic side (W m\(^{-2}\) K\(^{-1}\))

\(h_{o}\) :

Heat transfer coefficient between fluid phase and reactor wall in endothermic side (W m\(^{-2}\) K\(^{-1}\))

\(\Delta H_{f,i}\) :

Enthalpy of formation of component \(i\) (J mol\(^{-1}\))

\(j_{H}\) :

permeation rate of hydrogen through the Pd–Ag membrane(mol/s)

\(K\) :

Rate constant of dehydrogenation reaction (mol m\(^{-3}\) Pa\(^{-1}\) s\(^{-1}\))

\(k_{1}\) :

Rate constant for the 1st rate equation of methanol synthesis reaction (mol kg\(^{-1}\) s\(^{-1}\) bar\(^{-1/2}\))

\(k_{2}\) :

Rate constant for the 2nd rate equation of methanol synthesis reaction (mol kg\(^{-1}\) s\(^{-1}\) bar\(^{-1/2}\))

\(k_{3}\) :

Rate constant for the 3rd rate equation of methanol synthesis reaction (mol kg\(^{-1}\) s\(^{-1}\) bar\(^{-1/2}\))

\(k_{g}\) :

Mass transfer coefficient for component \(i\) (m s\(^{-1}\))

\(K\) :

Conductivity of fluid phase (W m\(^{-1}\) K\(^{-1}\))

\(K_{B}\) :

Adsorption equilibrium constant for benzene (Pa\(^{-1}\))

\(K_{i}\) :

Adsorption equilibrium constant for component \(i\) in methanol synthesis reaction (bar\(^{-1}\))

\(K_{p}\) :

Equilibrium constant for dehydrogenation reaction (Pa\(^{3}\))

\(K_{pi}\) :

Equilibrium constant based on partial pressure for component \(i\) in methanol synthesis reaction

\(K_{w}\) :

Thermal conductivity of reactor wall (W m\(^{-1}\) K\(^{-1}\))

\(L\) :

Reactor length (m)

\(M_{i}\) :

Molecular weight of component \(i\) (g mol\(^{-1}\))

\(N\) :

Number of components (N \(=\) 6 for methanol synthesis reaction, N \(=\) 3 for dehydrogenation reaction)

\(P\) :

Total pressure (for exothermic side: bar; for endothermic side: Pa)

\(P_{i}\) :

Partial pressure of component \(i\) (Pa)

\(r_{1}\) :

Rate of reaction for hydrogenation of CO (mol kg\(^{-1}\) s\(^{-1}\))

\(r_{2}\) :

Rate of reaction for hydrogenation of CO\(_{2}\) (mol kg\(^{-1}\) s\(^{-1}\))

\(r_{3}\) :

Rate of reversed water-gas shift reaction (mol kg\(^{-1}\) s\(^{-1}\))

\(r_{4}\) :

Rate of reaction for dehydrogenation of cyclohexane (mol m\(^{-3}\) s\(^{-1}\))

\(r_{i}\) :

Reaction rate of component \(i\) (for exothermic reaction: mol kg\(^{-1}\) s\(^{-1}\); for endothermic reaction: mol m\(^{-3}\) s\(^{-1}\))

\(R\) :

Universal gas constant (J mol\(^{-1}\) K\(^{-1}\))

\(R_{p}\) :

Particle radius (m)

Re :

Reynolds number

Sc \(_{i}\) :

Schmidt number of component \(i\)

\(T\) :

Temperature (K)

\(u\) :

Superficial velocity of fluid phase (m s\(^{-1}\))

\(U\) :

Overall heat transfer coefficient between exothermic and endothermic sides (W m\(^{-2}\) K\(^{-1}\))

\(v_{ci}\) :

Critical volume of component \(i\) (cm\(^{3}\) mol\(^{-1}\))

\(y_{i}\) :

Mole fraction of component \(i\) (mol mol\(^{-1}\))

\(z\) :

Axial reactor coordinate (m)

\(\mu \) :

Viscosity of fluid phase (kg m\(^{-1}\) s\(^{-1}\))

\(\rho \) :

Density of fluid phase (kg m\(^{-3}\))

\(\rho _{b}\) :

Density of catalytic bed (kg m\(^{-3}\))

\(\tau \) :

Tortuosity of catalyst

g:

In bulk gas phase

s:

At surface catalyst

0:

Inlet conditions

\(B\) :

Benzene

\(C\) :

Cyclohexane

\(i\) :

Chemical species

\(j\) :

Reactor side

\(k\) :

Reaction number index

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Authors and Affiliations

  1. Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, 71345 , Shiraz, Iran

    M. Bayat & M. R. Rahimpour

  2. Gas Center of Excellence, Shiraz University, 71345 , Shiraz, Iran

    M. R. Rahimpour

Authors
  1. M. Bayat
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  2. M. R. Rahimpour
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Correspondence to M. R. Rahimpour.

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Bayat, M., Rahimpour, M.R. Simultaneous hydrogen and methanol enhancement through a recuperative two-zone thermally coupled membrane reactor. Energy Syst 3, 401–420 (2012). https://doi.org/10.1007/s12667-012-0062-0

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