Chemical Engineering /

modelling / simulation

Methanol Synthesis

ENSIC-UFAZ

Christophe CASTEL
Dimitrios Meimaroglou
Content

1 Case Study. 2

2 Reaction scheme. 3

3 reactions rate and thermodynamics. 4

3.1 Reaction rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2 kinetics constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3 Equilibrium constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.4 Reactions enthalpies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.5 catalyst data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

4 Differential mass and heat balances. 6

1
1 Case Study.

We want to produce methanol from syngas. This gas phase reaction requires the design of a
catalytic reactor. What is the volume and the design of a catalytic piston reactor allowing to
treat 1000 Nm3 / h of a synthesis gas of composition:

ˆ CO : 22.5 %

ˆ H2 : 6 %

ˆ CO2 : 8 %

ˆ CH3OH : 0.5 %

ˆ H2O : 0 %

ˆ N2 : 0%

Different elements of discussion and decision-making could be analysed and studied:

ˆ kinetic model: is the equilibrium model sufficient?

ˆ Can the reactor be adiabatic? If not, what type of heat exchanger can we use?

ˆ What should ne tne feed temperature

ˆ What is the pressure inside the reactor ?

ˆ Safety issues ?

ˆ ...

2
2 Reaction scheme.

The synthesis of methanol from syngas can be expressed according to the following reaction
scheme:

CO + 2H2 *
) CH3 OH (2.1)
* CH3 OH + H2 O
CO2 + 3H2 ) (2.2)
* CO + H2 O
CO2 + H2 ) (2.3)
(2.4)

These three reactions are equilibrated non-isothermal reactions (exo- and endothermic).

3
3 reactions rate and
thermodynamics.

3.1 Reaction rates

The reaction rate of the different reactions are the following:
 
3/2
k1 KCO PCO PH2 − PCH3OH1/2
P KP1
r1 =  H2  (3.1)
1/2
(1 + KCO PCO + KCO2 PCO2 ) PH2 + KH2OH2 PH2O
 
3/2 PH2O PCH3OH
k2 KCO2 PCO2 PH2 − 3/2
PH2 KP2
r2 =   (3.2)
1/2
(1 + KCO PCO + KCO2 PCO2 ) PH2 + KH2OH2 PH2O
 
k3 KCO2 PCO2 PH2 − PH2O KP3
PCO

r3 =   (3.3)
1/2
(1 + KCO PCO + KCO2 PCO2 ) PH2 + KH2OH2 PH2O
(3.4)
These rates are expressed in mol / s / kg cata and partial pressures of the various compounds
in bar.

3.2 kinetics constants

The parameters k1 , k2 , k3 , KCO , KCO2 et KH20H2 are kinetics constants expressed among Ar-
rhenius laws :

E
k = k0 exp( )
RT
avec :

constants k0 E
k1 4.89e7 -63000
k2 1.09e5 -87500
k3 9.64e11 -152900
KCO 2.16e-5 46800
KCO2 7.05e-7 61700
KH2OH2 6.37e-9 84000

3.3 Equilibrium constants

PArameters KP1 , KP2 et KP3 are equilibrium constants expressed among :
A
KPi = 10 T −B
avec :

4
 constantes A B
KP1 5139 12.621
KP2 3066 10.592
KP3 -2073 -2.029

3.4 Reactions enthalpies

The reaction enthalpies are the following:

réaction enthalpie kJ/mol

1 -90.55
2 -49.43
3 41.12

3.5 catalyst data

ˆ density ρcata : 1770 kg/m3

ˆ apparent bed porosity  : 0.4

5
4 Differential mass and heat
balances.

The objective of this project is to write and solve the differential mass and heat balances within
the reactor. These balances must be written in mass flux (mol / s) and energy (W).

indice variable/compound
1 CO
2 H2
3 CO2
4 CH3 OH
5 H2 O
6 N2
7 T

dF (1)
= −(r1 − r3 )ρcata (1 − ) (4.1)
dV
dF (2)
= −(2r1 + 3r2 + r3 )ρcata (1 − ) (4.2)
dV
dF (3)
= −(r2 + r3 )ρcata (1 − ) (4.3)
dV
dF (4)
= −(−r1 − r2 )ρcata (1 − ) (4.4)
dV
dF (5)
= −(−r2 − r3 )ρcata (1 − ) (4.5)
dV
dF (6)
= 0 (4.6)
dV
PNreaction 2U
dT j=1 (rj (−∆Hj )) ρcata (1 − ) − Rtube (T − Tw )
= PNcomposes
dV Fi Cpi
i=1

(4.7)

avec :

ˆ Tw : wall temperature

ˆ U : heat exchange coefficient (W/m2 /K)

ˆ Cp : calorific capacity (J/mol/K)