Supporting Information
Methanol Production by Bi-Reforming
Bruno A.V. Santos, José M. Loureiro, A.M. Ribeiro, Ana E. Rodrigues,
Adelino F. Cunha*
Laboratory of Separation and Reaction Engineering,
Department of Chemical Engineering, Faculty of Engineering, University of Porto,
Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
Corresponding Author
*E-mail: afcunha@fe.up.pt. Telephone: +351-22-5081671. Fax: +351-22-5081674.
1
This supporting informations contain three tables and five figures, with physical data,
equations, and additional informations used for our calculations and to support the
discussion.
Table S1: Main physical properties (for ideal gas assumption) of the compounds involved in BMR.
C
Properties
CH4
CO2
H2O
CO
H2
 f H o / kJ·mol-1
-74.85
-393.51
-285.83
-110.54
0
0
-200.94
 f S o / J·K-1·mol-1
186.27
213.68
69.91
197.9
130.59
5.74
239.88
A
14.71
24.91
30.89
27.29
28.96
-0.4493
31.262
B
0.0724
0.0474
0.0079
0.0055
-0.0006
0.0355
0.00418
10 C
-1.375
-1.759
0.249
0.021
0.190
-1.308
-
(graphite)
CH3OH
Cp o / J·K-1·mol-1
5
* Cpº  A  B  T  C  T 2 (Fitted)
Table S2: Main reactions involved in BMR process.
Number
Reaction
Equilibrium
CH4 + CO2 ⇌ 2CO + 2H2
K1 
2
y CO
y H2 2  P  2


y CH 4 y CO2  P o 
2
CH4 + H2O ⇌ CO + 3H2
K2 
y CO y H3 2  P  2


y CH 4 y H 2O  P o 
3
CO+ H2O ⇌ CO2 + H2
1
K3 
y CO2 y H 2
y CO y H 2O
4
CH4 ⇌ C + 2H2
a C y H2 2  P 
K4 


y CH 4  P o 
5
2CO ⇌ C + CO2
K5 
a C y CO2  P o

2
y CO
 P
6
C + H2O ⇌ CO + H2
K6 
y CO y H 2  P 


a C y H 2O  P o 
7
CO + 2H2 ⇌ CH3OH
K7 
yCH 3OH  P o

yCO y H2 2  P
2






Table S3: Enthalpy, Entropy and Gibbs free energy of the reactions involved in methanol synthesis.
Reactions
 r H o / kJ·mol-1
 r S o / J·K-1·mol-1
o
-1
 r G 550
K / kJ·mol
CO + 2H2 ⇌ CH3OH
-91
-333
92
CO2 + 3H2 ⇌ CH3OH + H2O
-47
-380
162
CO + H2O ⇌ H2 + CO2
-41
77
-83
CO + 3H2 ⇌ CH4 + H2O
-206
-335
-22
2CO + 4H2 ⇌ (Me)2O + H2O
-248
-583
73
2CO + 4H2 ⇌ EtOH + H2O
-342
-567
-30
Figure S1: Primary energy and raw material resources.
3
Figure S2: Atmospheric CO2 concentration along the time [8].
Figure S3: Methanol Economy.
4
Figure S4: Free Gibbs energy changes of reaction (direct methanol synthesis from BMR) versus
temperature.
Figure S5: CO2 conversion for direct synthesis of methanol (at different water ratios) as function of
pressure (at 1300K).
5