Thermodynamic calculations for Syngas to Methanol

conversion
Sukaran Arora
September 9, 2016

CO Data
o
f Hgas,
298.15 K
o
Sgas,
298.15 K
A
B
C
D
E
F
G
H

-110.53
197.66
25.57
6.10
4.05
-2.67
0.13
-118
227.37
-110.53

kJ/mol
J/molK

All the above values are obtained from NIST database. Use the following relations for temperature
o and S o :
dependence of f Hgas
gas
o
o
f Hgas,
T (K) f Hgas, 298.15 K = A t + B

t2
t3
t4
1
+C +D E +F H
2
3
4
t

t3
1
t2
+D E 2+G
2
3
2t
o
o
where f Hgas, 298.15 K is the standard enthalpy of formation of CO at T = 298.15 K, Sgas,
T (K) is
the standard entropy of CO at T(K), and t = T(K)/1000.
o
Sgas,
T (K) = A ln(t) + B t + C

At T = 673 K or t = 0.673, we get the following values :

o
f HCO(g),
673 K
o
SCO(g),
673 K

-99.34
221.85

kJ/mol
J/molK

H2 Data
o
f Hgas,
298.15 K
o
Sgas,
298.15 K
A
B
C
D
E
F
G
H

0
130.68
33.07
-11.36
11.43
-2.77
-0.16
-9.99
-172.71
0

kJ/mol
J/molK

All the above values are obtained from NIST database. Using the same relations for temperature
o and S o
dependence of f Hgas
gas as above for CO, at T = 673 K or t = 0.673, we get the following
values :
o
f HH
2 (g), 673 K
o
SH
(g),
673 K
2

10.95
154.45

kJ/mol
J/molK

CH3 OH Data
o
f Hliq.,
298.15 K
o
Sliq., 298.15 K
CP, liq.
Tvap
lvap H o
lvap S o
CP, gas

-238.4
127.19
80
337.7
35.21
113
0.0749T(K) + 21.84

kJ/mol
J/molK
J/molK
K
kJ/mol
J/molK
J/molK

o
o
where f Hliq.,
298.15 K is the standard enthalpy of formation at 298.15 K, Sliq., 298.15 K is the standard entropy (J/molK) at 298.15 K, CP, liq. and CP, gas are the constant pressure heat capacities in
the respective phases, Tvap is the vaporization temperature, lvap H o is the latent heat of vaporization at Tvap , and lvap S o is the latent entropy of vaporization at Tvap . The relation for temperature
dependence of CP, gas is obtained by fitting the data obtained for CP, gas between 300 K and 700
K from NIST.

All the above values except vap S o (obtained from Wikipedia) are obtained from NIST database.
o and S o :
Use the following relations for temperature dependence of f Hgas
gas
!
ZT
Tvap 298.15
dT
l
o
+ vap H +
CP, gas
1000
1000

o
o
f Hgas,
T (K) = f Hliq., 298.15 K + CP, liq.

Tvap

o
o
Sgas,
T (K) = Sliq., 298.15 K + CP, liq. ln

!
ZT
Tvap
CP, gas
l
o
+ vap S +
dT
298.15
T
Tvap

At T = 673 K, we get the following values :

2

o
f HCH
3 OH(g), 673 K
o
SCH
3 OH(g), 673 K

-180.01
290.34

kJ/mol
J/molK

CO + 2 H2 CH3 OH
o
o
o
o
Hrxn,
673 K = f HCH3 OH(g), 673 K f HCO(g), 673 K 2 f HH2 (g), 673 K
o
o
o
o
Srxn,
673 K = SCH3 OH(g), 673 K SCO(g), 673 K 2 SH2 (g), 673 K

Substituting values obtained for f H o and S o for CO, H2 , and CH3 OH, we get the following
result :
o
Hrxn,
673 K = 102.58 kJ/mol
o
Srxn, 673 K = 240.4 J/mol K

Using the following relation to obtain Gorxn, T (K) :

o
o
Gorxn, T (K) = Hrxn,
T (K) T Srxn, T (K)
!
240.4
o
Grxn, 673 K = 102.58 673
1000

Gorxn, 673 K = 59.21 kJ/mol

Use the following relation to obtain equilibrium constant at 673 K :
o

K = expGrxn /RT
K = exp59.211000/(8.314673)
K = 2.54 105
For obtaining the equilibrium conversion, we write the following equations :
pCO = poCO (1 x)
!

pH2 = poCO

poH2
2x
poCO

= poCO (2 2x) = 2 poCO (1 x)

pCH3 OH = poCO x
K=

(pCH3 OH /po )
(pCO /po ) (pH2 /po )2

where po = 1 bar and poCO = 10/3 bar

K=

po
poCO

!2

x
4(1 x)3

2.54 105 (10/3)2 =

x
4(1 x)3

Solving the above equation gives :

x = xeq = 0.0011 or 0.1%