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Reaction Rate

Methanol is produced from carbon monoxide and hydrogen.


CO+2 H 2 CH 3 OH
Hydrogenation of carbon monoxide used to be viewed as the principal reaction. The present
view is that methanol is formed from CO2 over Cu catalyst. Only two of theses reactions are
linearly independent and define the equilibrium composition. These are hydrogenation of CO 2
(r1) and reverse water gas shift reaction (r2).
( r 1 ) :CO 2+ 3 H 2 CH 3 OH + H 2 O H rxn , 298 K =50 kJ /mol

( r 2 ) :CO 2+ H 2 CO+ H 2 O H rxn , 298 K =40 kJ /mol


Kinetic model is given by Vanden Buscshe and Froment (1996).

Arrhenius and vant Hoff equations are used in their reparametrized form :

k i=exp A i

E A ,i
RT

S 0n H 0n
K n=exp

R
RT

Parameter values in the kinetic model


k i= A exp

[ ]
B
RT

A
0.499
6.62e-11
3,453.38
1.07
1.22e10

B
17,197
12,4119
0
3,669
-94,765

Keq

ka
kb
kc
kd
ke
Ki

eq

A
B)
(
=10 T

K 1eq

3,066

10.592

K 2eq

2,073

2.029

Mass Balance
Component
CO
CO4
CH4
CH3OH
H2
H2O

Input
FCO,0
FCO2,0
FCH4,0
FCH3OH,0
FH2,0
FH2O,0

Output
FCO,0 + FH2,0 (x2)
FCO2,0 - FH2,0 (1/3x1-x2)
FCH4,0
FCH3OH,0 + FH2,0 (1/3x1)
FH2,0 - FH2,0 (x1-x2)
FH2O,0 + FH2,0 (1/3x1-x2)

X1 = conversion of H2 in reaction 1
X2 = conversion of H2 in reaction 2
Design Equiation
d X 1 3r 1
=
dW F H 2,0
d X2
r
= 2
dW F H 2,0
r

dX = F dW
Ao

W =14.520ton
3

p=1082 kg /m

Volume of catalyst=

14520 kg
=13.41m3
3
1082 kg/m

Rule of thumb: for tubular reactor with single phase reactant, L/D ratio is 10-30
L=30 D=30 0.102m=3.06 m

Volume per tube= D L


Volume per tube = (0.102)2 ( 3.06 )=0.025m 3
Number of tube
number of tube=

total bed volume


13.41m 3
=
=537 tube
bed volume per tube 0.025 m3

Shell Thickness
We use cylindrical vessel, to determine shell thickness we use equation from ASME Section VIII
t=

PR
+CA
(SE0.6 P)

Where
t

= Shell Thickness

= Pressure

= Inner Diameter Vessel

= allowable stress = 22,600 psi (ASME Code)

= Welding Efficiency = 0.85

= corrosion allowance = 0.125


t=

1146 x 44.29
+ 0.125=0.073 inch
22600 x 0.850.6 x 29

Head Thickness
We use Hemispherical Head because the pressure for our process very high
t=

PR
+CA
SE0,2 P

Where
t

= Head Thickness

= Pressure

= radius

= allowable stress = 22600 (ASME code for SB 167)

= Efficiency = 0.85

CA

= corrosion allowance = 0.125

The material which we used is Carbon Steel SA 167 because the material can be used with
temperature until 900 0F and the allowable stress is 16,000 psi (ASME Code).
t=

0.85 x 1146 x 44.29


+ 0.125=1.52 inch=0.037 m
22600 x 0.850.2 x 1146