Reaction Equations and Kinetics (directly taken from

http://www.che.cemr.wvu.edu/publications/projects/)

The first reactor is a steam methane reforming reactor. The reactions that take place in this

reactor are shown in Equations 1 and 2.

CH4  H 2O  CO  3H 2 (1)

CO  H 2 O  H 2  CO2 (2)

Equation 1 is the reforming reaction. It is highly endothermic and produces more moles of

products than reactants. This makes conversion favored by high temperatures and low pressures.

Equation 2 is the water-gas shift reaction. This reaction is exothermic, independent of pressure,

and favored by low temperatures. Both reactions are equilibrium limited and are controlled by

reaction kinetics shown in Equations 3-12.3 The catalyst used in these reactions is Rh/MgO on

Al2O3 support structure.

 PCO PH32 
r1  k 1  PCH 4 PH 2O   (3)
 K1 
 

 E 
k 1  A1 exp   1  (4)
 RT 

A1  1.275x10 8 (5)

E1  1.605x10 8 (6)

  26830 
K 1  exp   30.114  (7)
 T 

 PH PCO2 
r2  k 2  PCO PH 2O  2 
 (8)
 K2 
 2

 E 
k 2  A2 exp   2  (9)
 RT 

A2  1.466x10 3 (10)

E 2  6.713x10 7 (11)

 4400 
K 2  exp   4.036  (12)
 T 

In Equations 3-12, the reaction rate is in kmol/m3cat/s, the pressure is in bar, and the temperature

is in Kelvin. The activation energy units are J/kmol.

The second reaction in this system is the production of methanol from the syngas produced in

the steam-methane reforming reaction. Equations 13 and 14 detail the reactions that take place

in the production of methanol.

CO  2H 2  CH 3OH (13)

CO2  H 2  CO  H 2O (14)

Equation 13 is the desired reaction in the production of methanol. It is highly exothermic and

produces fewer moles than it reacts. This makes conversion favored by low temperatures and

high pressures. Equation 14 displays the water-gas shift reaction. Both reactions are equilibrium

limited and are controlled by reaction kinetics shown in Equations 15-20. The constants in the

reaction rate are taken from a case study conducted at 225°C.4

K CO K H2 2  pCO p H2 2  p MeOH / K eq 
r1  k1
1  K pCO  K CO2 pCO2  K H 2 p H 2 
3
(15)
CO

k1  1.064 (16)

K CO  12.52 (17)

K H 2  1.77 (18)
 3

K eq  9034 (19)

K CO2  39.62 (20)

In Equation 15, the reaction rate is in mol/g cat/h and the pressure is in atm.