Formox Process

The general chemical equation of Formox reaction:

2CH3OH + O2 2CH2O + 2H2O

Reactants Products

Table 1: Thermochemical data (at 298K and 1 bar)

Species i Gibbs Enthalpy Ai Bi Ci Di Ei
energy of energy of (103) (106) (10-5) (109)
formation, formation,
gf0 hf0
(kJ/mol) (kJ/mol)
CH3OH -2 -161.96 -200.66 2.211 12.216 -3.45 0 0

O2 -1 0 0 3.639 0.506 -0.227 -0.227 0

CH2O 2 -109.99 -115.97 2.264 7.022 -1.877 0 0

H2O 2 -228.57 -241.82 3.47 1.45 0 0.121 0

vi( )i 1 -353.2 -314.26 3.407 -0.00799 3.1510-6 46900 0

Table 2: Express the number of moles in terms of extent of reaction

Species Moles outlet Mole fraction

CH3OH 2-2 2 2
3+
O2 1- 1
3+
CH2O 2 2
3+
H2O 2 2
3+
Total 3+
Sample calculation
i) Production of formaldehyde at 1bar and 773.15K
-To calculate the changes Gibbs energy of reaction:
= vi(gf0)i of product(s) vi(gf0)i of reactant(s)
= 2(-228.57 kJ/mol) +2(-109.99 kJ/mol) 1(0 kJ/mol) 2(-161.96 kJ/mol)
= -353.20 kJ/mol

-To calculate the changes of enthalpy energy of reaction,

= vi(hf0)i of product(s) vi(hf0)i of reactant(s)
= 2(-241.82 kJ/mol) +2(-115.97 kJ/mol) 1(0 kJ/mol) 2(-200.66 kJ/mol)
= -314.26 kJ/mol

- Equilibrium constant of the reaction, K at 298K:

0

K298 = exp ( )

(353.20 103 /)
= exp ( (8.314)(298)
)

= 8.1763 x 1061

- Equilibrium constant of the reaction at T=773.15K

773.15 0
B C D E
ln( ) = [- + A(298) + (2982) + (2983)- 298 + 4 (2984) ]
298 2 3
1 1 773.15 B
(773.15 298) + A ln ( )+ (773.15 298)
298 2
C D 1 1 E
+ (773.152 2982) + (773.152 )+ (773.153 2983)
6 2 2982 12

773.15 (314.26x103 ) 0.00799 3.15x106

ln( ) = [- + (3.407)(298) + (2982) + (2983)
298 8.314 2 3
46900 1 1 773.15 0.00799
- ](773.15 298) + (3.407) ln ( )+ (773.15 298)
298 298 2

3.15x106 46900 1 1
+ (773.152 2982) + (773.152 )
6 2 2982
773.15
ln( ) = -77.6633
298

773.15
= 1.867 x 10-34
298

K773.15 = 1.527 x 1028

-Extent of reaction under temperature of 773.15 K and pressure of 1 bar
( )( )
K773.15 = ( Pv , y = mole fraction of respective component ; v = 1
)( )

From table 2 ,
2 2 2 2
( ) ( )
28 3+ 3+
1.527 x 10 = 22 2 1 1 (1)1
( ) ( )
3+ 3+

(2)4
= (3+)(22)2 (1)1
(1)1

= 0.999999
1.000

ii) Production of formaldehyde at 300bar and 773.15K

From table 2 ,
2 2 2 2
( ) ( )
28 3+ 3+
1.527 x 10 = 22 2 1 1 (300)1
( ) ( )
3+ 3+

(2)4
= (3+)(22)2 (1)1
(300)1

= 0.999999
1.000