REACTION 1 COMBUSTION

CH4+2O2 --> CO2 + 2H2O

Driving Force Term 1 5.85E+17 40.91073
-204000 8.314 -24536.9
Term 2 1 0
0 8.314 0

Adsorption Term 2 4.02E+05 12.9042

103500 8.314 12448.88
Term 3 5.08E+04 10.8357
66200 8.314 7962.473

REACTION 2
CH4 + H2O --> CO + 3 H2
Driving Force Term 1 4.23E+15 35.9798
-240100 8.314 -28879
Term 2 7.34E+02

7.34E+02 6.5984
8.314 0

Adsorption Term 2 8.23E-05 -9.4051

-70650 8.314 -8497.71
Term 3 6.12E-09 -18.9117
-82900 8.314 -9971.13
Term 4 6.65E-04 -7.3157
-38280 8.314 -4604.28
Term 5 1.77E+05 12.0839
88680 8.314 10666.35
R3
CO + H2O --> CO2 + H2
Driving Force Term 1 1.96E+06 14.4859
-67130 8.314 -8074.33
Term 2 1.552E+08

1.552E+08 18.85996
8.314 0

R4
CH4 + 2H2O --> CO2 + 4 H2
Driving Force Term 1 1.02E+15 34.5586
-243900 8.314 -29336.1
Term 2 14088.39779

14088.39779 9.5531
8.314 0
 A B T Exp 1/Exp
5.75E+12 -11476 100 8.32E-38 1.20E+37
200 6.92E-13 1.45E+12
300 1.40E-04 7.14E+03
400 1.99E+00 5.01E-01
500 6.19E+02 1.62E-03
600 2.84E+04 3.52E-05
700 4.36E+05 2.29E-06
800 3.39E+06 2.95E-07
900 1.67E+07 6.00E-08
1000 5.97E+07 1.68E-08
1100 1.69E+08 5.90E-09

2nd reaction A B T 1st Exp 2nd Exp

1st Exp in Num 4.23E+15 -240100 100 1.61E-110 8.32E-38
200 8.24E-48 6.92E-13
300 6.59E-27 1.40E-04
400 1.87E-16 1.99E+00
2nd Exp in Den 5.75E+12 -11476 500 3.48E-10 6.19E+02
600 5.28E-06 2.84E+04
700 5.11E-03 4.36E+05
Aspen Mod 7.35E+02 -17403 800 8.88E-01 3.39E+06
900 4.90E+01 1.67E+07
1000 1.21E+03 5.97E+07
1100 1.68E+04 1.69E+08

3rd reaction A B T 1st Exp 2nd Exp

1st Exp in Num 1.96E+06 -67130 100 1.68E-29 1.77E+18
200 5.73E-12 1.49E+08
300 4.00E-06 6.55E+04
400 3.35E-03 1.37E+03
2nd Exp in Den 1.26E-02 4639 500 1.90E-01 1.35E+02
600 2.80E+00 2.87E+01
700 1.91E+01 9.52E+00
Aspen Mod 1.55E+08 -12713.3 800 8.09E+01 4.16E+00
900 2.48E+02 2.18E+00
1000 6.09E+02 1.30E+00
1100 1.27E+03 8.55E-01
4th reaction A B T 1st Exp 2nd Exp
1st Exp in Num 1.02E+15 -243900 100 4.02E-113 7.12E-84
200 2.02E-49 7.18E-37
300 3.47E-28 3.34E-21
400 1.44E-17 2.28E-13
2nd Exp in Den 7.24E+10 -21646 500 3.37E-11 1.14E-08
600 5.95E-07 1.56E-05
700 6.43E-04 2.69E-03
Aspen Mod 1.41E+04 -7690.06 800 1.21E-01 1.28E-01
900 7.12E+00 2.60E+00
1000 1.85E+02 2.88E+01
1100 2.67E+03 2.06E+02
1st/2nd Aspen Mod
1.93E-73 1.93E-73
1.19E-35 1.19E-35
4.71E-23 4.71E-23
9.36E-17 9.36E-17
5.62E-13 5.62E-13
1.86E-10 1.86E-10
1.17E-08 1.17E-08
2.62E-07 2.62E-07
2.94E-06 2.94E-06
2.03E-05 2.03E-05
9.89E-05 9.89E-05

1st/2nd Aspen Mod

9.49E-48 9.49E-48
3.84E-20 3.84E-20
6.11E-11 6.11E-11
2.44E-06 2.44E-06
1.41E-03 1.41E-03
9.74E-02 9.74E-02
2.01E+00 2.01E+00
1.95E+01 1.95E+01
1.14E+02 1.14E+02
4.67E+02 4.67E+02
1.48E+03 1.48E+03
1st/2nd Aspen Mod
5.64E-30 5.64E-30
2.82E-13 2.82E-13
1.04E-07 1.04E-07
6.30E-05 6.30E-05
2.95E-03 2.95E-03
3.82E-02 3.82E-02
2.39E-01 2.39E-01
9.42E-01 9.42E-01
2.74E+00 2.74E+00
6.44E+00 6.44E+00
1.30E+01 1.30E+01
 62 1607.04
12.99876
1492.464
125

20889 3.00E+09
0.002814

4.18E+07
7.936508
-2646 126.12
0.24982873 2.520672
0.00198088
 11502
7.668 1.013619

7.923302
0.315084
2.520672
REACTION 2
CH4 + H2O --> CO + 3 H2
Driving Force Term 1 1.96E+06 14.4859
-67130 8.314 -8074.33
Term 2 3.40E-07

3.40E-07 -14.8943
8.314 0

R3
CO + H2O --> CO2 + H2
Driving Force Term 1 1.02E+15 34.5586
-243900 8.314 -29336.06
Term 2 8.095E+16

8.095E+16 38.9326
8.314 0

R4
CH4 + 2H2O --> CO2 + 4 H2
Driving Force Term 1 5.85E+17 40.9107
-204000 8.314 -24536.926
Term 2 8082872.928

8082872.928 15.9053
8.314 0

2nd reaction A B T
1st Exp in Num 1.96E+06 -67310 100
200
300
400
2nd Exp in Den 5.75E+12 -11476 500
600
700
Aspen Mod 3.40E-07 3380.02 800
900
1000
 1100

3rd reaction A B T
1st Exp in Num 1.02E+15 -243900 100
200
300
400
2nd Exp in Den 1.26E-02 4639 500
600
700
Aspen Mod 8.10E+16 -33975.06 800
900
1000
1100

4th reaction A B T
1st Exp in Num 5.85E+17 -204000 100
200
300
400
2nd Exp in Den 7.24E+10 -21646 500
600
700
Aspen Mod 8.08E+06 -2890.925668 800
900
1000
1100
1st Exp 2nd Exp 1st/2nd Aspen Mod
1.35E-29 8.32E-38 1.62E+08 1.62E+08
5.14E-12 6.92E-13 7.43E+00 7.43E+00
3.72E-06 1.40E-04 2.66E-02 2.66E-02
3.17E-03 1.99E+00 1.59E-03 1.59E-03
1.82E-01 6.19E+02 2.93E-04 2.93E-04
2.70E+00 2.84E+04 9.51E-05 9.51E-05
1.85E+01 4.36E+05 4.25E-05 4.25E-05
7.87E+01 3.39E+06 2.32E-05 2.32E-05
2.42E+02 1.67E+07 1.45E-05 1.45E-05
5.96E+02 5.97E+07 9.99E-06 9.99E-06
1.24E+03 1.69E+08 7.34E-06 7.34E-06

1st Exp 2nd Exp 1st/2nd Aspen Mod

4.02E-113 1.77E+18 2.27E-131 2.27E-131
2.02E-49 1.49E+08 1.36E-57 1.36E-57
3.47E-28 6.55E+04 5.30E-33 5.30E-33
1.44E-17 1.37E+03 1.05E-20 1.05E-20
3.37E-11 1.35E+02 2.50E-13 2.50E-13
5.95E-07 2.87E+01 2.07E-08 2.07E-08
6.43E-04 9.52E+00 6.75E-05 6.75E-05
1.21E-01 4.16E+00 2.91E-02 2.91E-02
7.12E+00 2.18E+00 3.26E+00 3.26E+00
1.85E+02 1.30E+00 1.42E+02 1.42E+02
0.00E+00 0.00E+00 #DIV/0! 0.00E+00

1st Exp 2nd Exp 1st/2nd Aspen Mod

1.60E-89 7.12E-84 2.25E-06 2.25E-06
3.06E-36 7.18E-37 4.27E+00 4.27E+00
1.76E-18 3.34E-21 5.28E+02 5.28E+02
1.34E-09 2.28E-13 5.87E+03 5.87E+03
2.85E-04 1.14E-08 2.49E+04 2.49E+04
1.02E+00 1.56E-05 6.53E+04 6.53E+04
3.50E+02 2.69E-03 1.30E+05 1.30E+05
2.80E+04 1.28E-01 2.18E+05 2.18E+05
8.45E+05 2.60E+00 3.26E+05 3.26E+05
1.29E+07 2.88E+01 4.49E+05 4.49E+05
1.20E+08 2.06E+02 5.84E+05 5.84E+05
REACTION 2
CH4 + H2O --> CO + 3 H2
Driving ForTerm 1 1.00E+00 0
0 8.314 0
Term 2 1.74E-13

1.74E-13 -29.3802
8.314 0

2nd reaction A B T 1st Exp 2nd Exp 1st/2nd

1st Exp in 1.00E+00 0 100 1.00E+00 8.32E-38 1.20E+37
200 1.00E+00 6.92E-13 1.45E+12
300 1.00E+00 1.40E-04 7.14E+03
400 1.00E+00 1.99E+00 5.01E-01
2nd Exp in 5.75E+12 -11476 500 1.00E+00 6.19E+02 1.62E-03
600 1.00E+00 2.84E+04 3.52E-05
700 1.00E+00 4.36E+05 2.29E-06
Aspen Mo 1.74E-13 11476.00 800 1.00E+00 3.39E+06 2.95E-07
900 1.00E+00 1.67E+07 6.00E-08
1000 1.00E+00 5.97E+07 1.68E-08
1100 1.00E+00 1.69E+08 5.90E-09
 2.718282

Aspen Mod
1.20E+37
1.45E+12
7.14E+03 101324 1.030E-01 1.017E-06
5.01E-01 1.027E-01 1.014E-06
1.62E-03 6.239E-02 6.157E-07
3.52E-05 1.276E-02 1.259E-07
2.29E-06 2.638E+03 2.604E-02
2.95E-07 1.938E+01 1.913E-04
6.00E-08
1.68E-08
5.90E-09
REACTION 2
CH4 + H2O --> CO + 3 H2
Driving Force Term 1 6.00E+13 31.7254
230100 8.314 27676.21
Term 2 3.00E-09 -19.6247
17036 8.314 2049.07
2nd reaction Atm to Pa 101325
Temp 900 C
1173 K
Gas constant 8.314
Partial pressure Atm Pa
CH4 0.3 30397.5
H2O 0.4 40530
H2 0.1 10132.5
CO 0.2 20265

Beretta 2009

K-SR Calculations

ki 1.03E-01 mol/gcat-s-atm
ki 1.04E+04 mol/gcat-s-pa

Ea 92000 kJ/kmol

K-SR= 0.832347

Driving force

Eta-SR Kp-SR/Keq

Kp-SR 17111259

Keq-SR from Nezhad 2009 5.75*10^12 exp(-11476/T)

be
1.61076
1.02981
Gas Constant 8.314 KJ/kmol K
Partial pressures
Atm Pa 101325
P-CH4 0.2 20265 0.05
P-O2 0.05 5066.25 0.01
P-CO 0.1 10132.5 0.3
P-CO2 0.1 10132.5 0.02
P-H2 0.3 30397.5 0.57
P-H2O 0.25 25331.25 0.05

1 101325

Temperature 750 C
1023 K

Adsorption
From Paper From Aspen
Oxygen Oxygen
kads 873 K 5.461 1/atm kads -9.8285 1/atm
DelHads -73000 KJ/kmol DelHads -8780.37 KJ/kmol

H2O H2O
kads 873 K 390.1 1/atm A -5.5597 1/atm
DelHads -16000 KJ/kmol B -1924.46 KJ/kmol

CO CO
kads 873 K 211.4 1/atm kads -6.1723 1/atm
DelHads -37000 kJ/kmol DelHads -4450.32 kJ/kmol

1st Equation Total Oxidation

From Paper From Aspen
k1 873 K 1.030E-01 mol / (atm gcat s) Kinetic Term k1 1.017E-06 kmol/kgcat s Pa
Ea1 92000 KJ/kmol Ea1 92000 KJ/kmol

Den1 15.8635 Den1 15.8635

K1 * P-CH4 / (1 + K-H2O * P-H2O)
R1-Toxd 3.2558E-08 mol/gcat s R1-Toxd 3.2558E-08 mol/gcat s

2nd Equation Steam Reforming

From Paper From Aspen
k2 873 K 1.027E-01 mol / (atm gcat s) Kinetic Term k2 1.014E-06 kmol/kgcat s Pa
Ea2 92000 KJ/kmol Ea2 92000 KJ/kmol

ko,eq-SR from Nezhad 5.75E+12 ko -52.4324

Ea -11476 Ea -11476

Den2 1.2728 Den2 1.2728

K1 * P-CH4 / (1 + K-H2O * P-H2O)
R2-SMR 3.2368E-07 mol/gcat s R2-SMR 4.0460E-07 mol/gcat s
(B44*EXP(-B45/($B$1*$B$14)))*B4*(1-(B6*B8^3/(B4*B9))/(B47*EXP(B48/$B$14)))/B50
(H44*EXP(-H45/($B$1*$B$14)))*C9*(1-C6*C8^3/(C4*C9)*EXP(H47+H48/$B$14))/H50

3rd Equation Direct WGS

From Paper From Aspen
k3 873 K 6.239E-02 mol / (atm gcat s) Kinetic Term k3 6.157E-07 kmol/kgcat s Pa
Ea3 25000 KJ/kmol Ea3 25000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02 ko 4.3741

Ea 4639 Ea -4639

Den3 251.6520 Den3 251.6520

K1 * P-CH4 / (1 + K-H2O * P-H2O)
R3-WGS -7.1852E-08 mol/gcat s R3-WGS -7.1852E-08 mol/gcat s
(B58*EXP(-B59/($B$1*$B$14)))*B9*(1-(B7*B8/(B6*B9))/(B61*EXP(B62/$B$14)))/B64
(H58*EXP(-H59/($B$1*$B$14)))*C9*(1-C7*C8/(C6*C9)*EXP(H61+H62/$B$14))/H64

4th Equation Reverse WGS

From Paper From Aspen
k4 873 K 1.276E-02 mol / (atm gcat s) Kinetic Term k4 1.259E-07 kmol/kgcat s Pa
Ea4 62000 KJ/kmol Ea4 62000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02 ko -4.3741

Ea 4639 Ea 4639

R4-RWGS 1.8678E-08 mol/gcat s R4-RWGS 1.8678E-08 mol/gcat s

(B72*EXP(-B73/($B$1*$B$14)))*B7*(1-(B6*B9/(B7*B8))*(B75*EXP(B76/$B$14)))
(H72*EXP(-H73/($B$1*$B$14)))*C7*(1-C6*C9/(C7*C8)*EXP(H75+H76/$B$14))

5th Equation H2 Oxidation

From Paper From Aspen
k5 873 K 2.638E+03 mol / (atm gcat s) Kinetic Term k5 2.604E-02 kmol/kgcat s Pa
Ea5 62000 KJ/kmol Ea5 62000 KJ/kmol

R5-H2oxd 5.402E-01 mol/gcat s R5-H2oxd 5.4019E-01 mol/gcat s 1.663246

6th Equation CO Oxidation

From Paper From Aspen
k6 873 K 1.938E+01 mol / (atm gcat s) Kinetic Term k6 1.913E-04 kmol/kgcat s Pa
Ea6 76000 KJ/kmol Ea6 76000 KJ/kmol

R6-COoxd 2.551E-04 mol/gcat s R6-COoxd 2.551E-04 mol/gcat s

Gas Constant 8.314 KJ/kmol K
Partial pressures
Atm Pa 101325
P-CH4 0.05 5066.25
P-O2 0.01 1013.25
P-CO 0.3 30397.5
P-CO2 0.02 2026.5
P-H2 0.57 57755.25
P-H2O 0.05 5066.25

1 101325

Temperature 750 C
1023 K

Adsorption
From Paper
Oxygen
kads 873 K 5.461 1/atm
DelHads -73000 KJ/kmol

H2O
kads 873 K 390.1 1/atm
DelHads -16000 KJ/kmol

CO
kads 873 K 211.4 1/atm
DelHads -37000 kJ/kmol

1st Equation Total Oxidation

From Paper
k1 873 K 1.030E-01 mol / (pa gcat s)
Ea1 92000 KJ/kmol

Den1 3.9727

R1-Toxd 2.635E-03

2nd Equation SMR

From Paper
k2 873 K 1.027E-01 mol / (pa gcat s)
Ea2 92000 KJ/kmol

ko,eq-SR from Nezhad 5.75E+12 bar^2

 Ea -11476 1/K
7.7225E+07 Keq cal
Den2 1.8183

R2-SMR -1.695E+01

3rd Equation Direct WGS

From Paper
k3 873 K 6.239E-02 mol / (pa gcat s)
Ea3 25000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02

Ea 4639

Den3 15.7824

R3-WGS 3.738E-01

4th Equation Reverse WGS

From Paper
k4 873 K 1.276E-02 mol / (pa gcat s)
Ea4 62000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02

Ea 4639

R4-RWGS -9.621E-03

5th Equation H2 Oxidation

From Paper
k5 873 K 2.638E+03 mol / (pa gcat s)
Ea5 62000 KJ/kmol

R5-H2oxd 1.040E+05

6th Equation CO Oxidation

From Paper
k6 873 K 1.938E+01 mol / (pa gcat s)
Ea6 76000 KJ/kmol
R6-COoxd 7.753E+01
From Aspen
Oxygen
kads -9.8285 1/Pa
DelHads -8780.37 KJ/kmol

H2O
A -5.5597 1/Pa 3.97270889
B -1924.46 KJ/kmol 3.97270889

CO
kads -6.1723 1/Pa
DelHads -4450.32 kJ/kmol

From Aspen
Kinetic Term k1 1.030E-01 kmol/kgcat s Pa
Ea1 92000 KJ/kmol

Den1 3.9727

R1-Toxd 2.635E-03

From Aspen
Kinetic Term k2 1.027E-01 kmol/kgcat s Pa
Ea2 92000 KJ/kmol

A -52.4324 29.3802
 B -11476 -11476
2.275042E-28 7.7225E+07
Den2 1.8183

R2-SMR 5.739E-03
(B44*EXP(-B45/($B$1*$B$14)))*C4*(1-(C6*C8^3/(C4*C9))/(B47*EXP(B48/$B$14)*$D$3^2)
(H44*EXP(-H45/($B$1*$B$14)))*C9*(1-C6*C8^3/(C4*C9)*EXP(H47+H48/$B$14))/H50

From Aspen
Kinetic Term k3 6.239E-02 kmol/kgcat s Pa
Ea3 25000 KJ/kmol

A 4.3741
B -4639

Den3 15.7824

R3-WGS 3.738E-01

From Aspen
Kinetic Term k4 1.276E-02 kmol/kgcat s Pa
Ea4 62000 KJ/kmol

A -4.3741
B 4639

R4-RWGS -9.621E-03

From Aspen
Kinetic Term k5 2.638E+03 kmol/kgcat s Pa
Ea5 62000 KJ/kmol

R5-H2oxd 1.040E+05

From Aspen
Kinetic Term k6 1.938E+01 kmol/kgcat s Pa
Ea6 76000 KJ/kmol
R6-COoxd 7.753E+01
)/(B47*EXP(B48/$B$14)*$D$3^2))/B50
*EXP(H47+H48/$B$14))/H50
Gas Constant 8.314 KJ/kmol K
Partial pressures
Bar Pa 100000
P-CH4 0.2 20000
P-O2 0.05 5000
P-CO 0.1 10000
P-CO2 0.1 10000
P-H2 0.3 30000
P-H2O 0.25 25000

1 100000

Temperature 750 C
1023 K

Adsorption
From Paper
Methane (Combustion)
kads 4.02E+05 1/bar
DelHads 103500 KJ/kmol

Oxygen (Combustion)
kads 5.08E+04 bar^-0.5
DelHads 66200 KJ/kmol

Methane (Reforming)
kads 6.64E-04 1/bar
DelHads -38280 KJ/kmol

CO
kads 8.23E-05 1/bar
DelHads -70650 KJ/kmol

H2
kads 6.12E-09 1/bar
DelHads -82900 kJ/kmol

H2O
kads 1.77E+05 bar
DelHads 88680 kJ/kmol

1st Equation Total Oxidation

From Paper
k1 5.852E+17 (kmol / kgcat hr) / bar^1.5
Ea1 204000 KJ/kmol
 Den1 37.8115

R1-Toxd 1.4824E+05 kmol / kgcat hr

2nd Equation SMR to CO

From Paper
k2 4.225E+15 (kmol / kgcat hr) bar^0.5
Ea2 240000 KJ/kmol

ko,eq-SR from Nezhad 5.75E+12 bar^2

Ea -11476 1/K

Den2 29.3393
Ke,2 7.72E+07
R2-SMR 8.1216E+01 kmol / kgcat hr

3rd Equation WGS

From Paper
k3 6.239E-02 mol / (atm gcat s)
Ea3 25000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02

Ea 4639

Den3 1.0000

R3-WGS -1.8082E-05 kmol / kgcat hr

4th Equation SMR to CO2

From Paper
k4 1.276E-02 mol / (atm gcat s)
Ea4 62000 KJ/kmol

ko,eq-WGS from Nezhad 1.26E-02

Ea 4639

R4-RWGS 1.8678E-08 kmol / kgcat hr

 0.05
0.01
0.3
0.02
0.57
0.05

Adsorption
From Aspen
Methane (Combustion)
kads 1.3913 1/Pa
DelHads -12448.88 KJ/kmol

Oxygen (Combustion)
kads 5.0792 Pa^-0.5
DelHads -7962.47 KJ/kmol

Methane (Reforming)
kads -18.8302 1/Pa
DelHads 4604.28 KJ/kmol

CO
A -20.9181 1/Pa
B 8497.71 KJ/kmol

H2
kads -30.4246 1/Pa
DelHads 9971.13 kJ/kmol

H2O
kads 12.0839 Pa
DelHads -10666.35 kJ/kmol

From Aspen
Kinetic Term k1 5.852E+12 (kmol / kgcat hr) / bar^1.5
Ea1 204000 KJ/kmol
 Den1 37.8115

R1-Toxd 1.4824E+05 kmol / kgcat hr

From Aspen
Kinetic Term k2 4.225E+10 (kmol / kgcat hr) bar^0.5
Ea2 240000 KJ/kmol

ko -52.4061
Ea -11476

Den2 29.3393
Ke,2 2.34E-28
R2-SMR 2.5683E-06 kmol / kgcat hr
(B56*EXP(-B57/($B$1*$B$14)))/B8^2.5*(B4*B9-B8^3*B6/(B59*EXP(B60/$B$14)))/B62
(H56*EXP(-H57/($B$1*$B$14)))/C8^2.5*(C4*C9-C8^3*D6*EXP(H59+H60/$B$14))/H62

From Aspen
Kinetic Term k3 6.239E-07 kmol/kgcat s Pa
Ea3 25000 KJ/kmol

ko 4.3741
Ea -4639

Den3 1.1736

R3-WGS -1.5407E-05 kmol / kgcat hr

From Aspen
Kinetic Term k4 1.276E-07 kmol/kgcat s Pa
Ea4 62000 KJ/kmol

ko -4.3741
Ea 4639

R4-RWGS 1.8678E-08 kmol / kgcat hr

EXP(B60/$B$14)))/B62
H59+H60/$B$14))/H62
1.663246
Gas Constant 8.314 KJ/kmol K
Partial pressures
Bar Pa 100000
P-CH4 0.2 20000 0.05
P-O2 0.05 5000 0.01
P-CO 0.1 10000 0.3
P-CO2 0.1 10000 0.02
P-H2 0.3 30000 0.57
P-H2O 0.25 25000 0.05

1 100000

Temperature 750 C
1023 K

Adsorption Adsorption
From Paper From Aspen
Methane (Combustion) Methane (Combustion)
kads 1.26E-01 1/bar A -13.5844 1/Pa
DelHads 27300 KJ/kmol B 3283.62

Oxygen (Combustion) Oxygen (Combustion)

kads 7.87E-07 1/bar A -25.5680 1/Pa
DelHads 92800 KJ/kmol B 11161.90

Methane (Reforming) Methane (Reforming)

kads 6.65E-04 1/bar A -18.8286 1/Pa
DelHads 38280 KJ/kmol B 4604.28

CO CO
kads 8.23E-05 1/bar 0.33337811 A -20.9181 1/Pa 3.33378110458944E-06
DelHads 70650 KJ/kmol B 8497.71

H2 H2
kads 6.12E-09 1/bar 0.000104664 A -30.4246 1/Pa 0.000000001
DelHads 82900 kJ/kmol B 9971.13

H2O H2O
kads 1.77E-05 bar A 0.5710 Pa 5.24549392419523E-05
DelHads -88680 kJ/kmol B -10666.35

1st Equation Total Oxidation

From Paper From Aspen
k1 1st term 2.920E+06 kmol/(kgcat bar^2 h) 8.111E+02 Kinetic Term k1 1st term 8.111E-08 kmol/(kgcat Pa^2 s)
Ea1 1st term 86000 KJ/kmol Ea1 1st term 86000 KJ/kmol

k1 2nd term 2.46E+06 kmol/(kgcat bar^2 h) 6.833E+02 k1 2nd term 6.833E-08 kmol/(kgcat Pa^2 s)
Ea1 2nd term 86000 KJ/kmol Ea1 2nd term 86000 KJ/kmol

Den1 1.6265 Den1 1.6265

R1-Toxd 1st term 4.4829E-01 kmol / kgcat hr R1-Toxd 1st term 4.4829E-01 kmol / kgcat hr
R1-Toxd 1st term 6.1426E-01 kmol / kgcat hr R1-Toxd 1st term 6.1426E-01 kmol / kgcat hr

Checked OK
2nd Equation SMR to CO
From Paper From Aspen
k2 4.225E+15 kmol bar^0.5/(kgcat h) 1.174E+12 Kinetic Term k2 3.711E+14 kmol Pa^0.5/(kgcat s)
Ea2 240100 KJ/kmol Ea2 240100 KJ/kmol

ko,eq-SR 1.20E+13 bar^2 ko (paper) 30.1140 From Paper

Ea 26830 1/K Ea (paper) -26830 From Paper
Ke,2 48.7749 Ke,2 48.7749 bar^2 From Paper
11525.27536 5972554816
7.708028286 A -53.1399
46.81187209 B 26830
50.57317563 Ke,2 (Aspen) 2.050234E-12 Pa^2 From Aspen
Driving Force 2nd term 5.535633E-05 Driving Force 2nd term 1.316923E+29

Den2 1.0928 2321.757779 5.535633E-05 Den2 1.0928

2.039456321 553563.30274 Ke,2
R2-SMR 2.1527E+03 kmol / kgcat hr R2-SMR 2.1525E+03 kmol / kgcat hr
47099.22624 ((B59*EXP(-B60/($B$1*$B$14)))/B8^2.5)*(B4*B9-B8^3*B6/(B62*EXP(-B63/$B$14)))/B71
13.0831184 ((H59*EXP(-H60/($B$1*$B$14)))/C8^2.5)*(C4*C9-C8^3*C6*EXP(H66+H67/$B$14))/H71
0.049944644
3rd Equation WGS 0.049944644
From Paper From Aspen
k3 1.020E+15 kmol bar^0.5/(kgcat h) Kinetic Term k3 8.960E+13 kmol Pa^0.5/(kgcat s)
Ea3 243900 KJ/kmol Ea3 243900 KJ/kmol

ko,eq-SR 2.12E+11 bar^2 ko (paper) 26.0780 From Paper

Ea 22430 1/K Ea (paper) -22430 From Paper
Ke,2 63.5795 Ke,2 63.5795 bar^2 From Paper

A -49.1039
B 22430
Ke,2 (Aspen) 1.572834E-12 Pa^2 From Aspen
Driving Force 2nd term 0 Driving Force 2nd term #VALUE!

Den3 1.0928 24245.43624 Den3 1.0928

6.734843401
R3-WGS 2.7706E+02 kmol / kgcat hr 63.57951327 R3-WGS 2.7704E+02 kmol / kgcat hr
1.57283E-12 (B79*EXP(-B80/($B$1*$B$14)))/B8^3.5*(B4*B9^2-B8^4*B7/(B82*EXP(-B83/$B$14)))/B91
(H79*EXP(-H80/($B$1*$B$14)))/C8^3.5*(C4*C9^2-C8^4*C7*EXP(H86+H87/$B$14))/H91

4th Equation SMR to CO2

From Paper From Aspen
k4 1.955E+06 kmol/(kgcat bar h) Kinetic Term k4 5.431E-03 kmol/(kgcat Pa s)
Ea4 67130 KJ/kmol Ea4 67130 KJ/kmol

ko,eq-SMR to CO2 1.77E-02 --- ko (paper) -4.0360 From Paper

Ea -4400 1/T Ea (paper) 4400 From Paper
Ke,2 1.3035 Ke,2 1.3035 bar^2 From Paper

A 4.0360
B -4400
Ke,2 (Aspen) 0.767148205 Pa^2 From Aspen
Driving Force 2nd term 9.82E+23 Driving Force 2nd term #VALUE!

Den3 1.0928 2433.474768 Den3 1.0928

6.75965E-11
R4-RWGS 4.4217E+00 kmol / kgcat hr R4-RWGS 4.4213E+00 kmol / kgcat hr
(B99*EXP(-B100/($B$1*$B$14)))/B8*(B6*B9-B8*B7/(B102*EXP(-B103/$B$14)))/B111
(H99*EXP(-H100/($B$1*$B$14)))/C8*(C6*C9-C8*C7*EXP(H102+H103/$B$14))/H111

Dudukovic 2007 LHHW

Forzatti 2009 LHHW corrected
 Starting mol/hr Start Temp
CH4 O2 H2 CO CO2 H2O Inerts CH4:O2 K
1 10000 4000 1000 1 1 1 1 2.5 973
2 10000 4000 1000 1 1 1 1 2.5 973
3 10000 4000 800 1 1 1 1 2.5 973
4 10000 4000 500 1 1 1 1 2.5 973
5 10000 4000 200 1 1 1 1 2.5 973
6 10000 5000 1000 1 1 1 1 2 973
7 10000 5000 800 1 1 1 1 2 973
8 10000 5000 500 1 1 1 1 2 973
9 10000 5000 200 1 1 1 1 2 973
10 10000 5000 200 1 1 1000 1 2 973
11 10000 5000 200 1 1 3000 1 2 973
12
13
14
15
16

1.721311 1.833333
36.28
13.14 1.05574
10.9

700
436234.5 0.0002706805
9.517045 9.4850254419
0.002692 0.0025674114
Pressure Approx Cat Wt Outlet mol/hr M
bar to Equilibrium CH4 O2 H2 CO CO2 H2O Inerts Value
1 6000 3218 17.5 13881 6280 502 682.8 1 1.973
2 3000 4059 1.8 11679 5089 853 1204 1 1.822
2 3000 4041 1.7 11534 5107 853 1186 1 1.792
5 1500 5175 0 8276 3527 1300 1876 1 1.445
15 500 6244 0 5147 2076 1682 2565 1 0.922
1 10000 2197 8.1 15345 6885 920 1262 1 1.848
2 4000 3164.4 0.8 12623 5522 1315 1850 1 1.654
5 1500 4427 0.1 9015 3780 1795 2633 1 1.295
15 500 5597 0 5597.8 2213 2191 3408 1 0.774
15 500 5456 0 6188 2188 2347 4099 1 0.847
15 500 5185 0.1 7302 2159 2658 5528 1 0.964
#DIV/0!

Ch
2.500

2.000

1.500
5000 TPD Methanol CO + 2H2 --> CH3OH
156250 kmol/day methanol CH4 + 0.5O2 --> CO + 2H2 1.000
156250 kmol/day CH4
0.0018084491 kmol/ms CH4 0.500
1.8084490741 gmol/ms CH4
148.292824074 lit/ms CH4 0.000
0 2 4 6
Va
148 lit
148000 cm3
10 10 cm thick
138 dia cm
149495
 Rgibbs

CH4 O2 H2 CO CO2 H2O Inerts

3214 13873 6271 516 700

6396 5443 1972 1633 2765

Chart Title
7000

6000

5000

4000

3000

2000

1000

0
2 4 6 8 10 12 14 16
Val ue CH4
Gas Constant 8.314 KJ/kmol K
Partial pressures
Bar Pa 100000
P-CH4 0.2 20000
P-O2 0.05 5000
P-CO 0.1 10000
P-CO2 0.1 10000
P-H2 0.3 30000
P-H2O 0.25 25000

1 100000

Temperature 750 C
1023 K

Adsorption
From Paper
Methane (Combustion)
kads 1.26E-01 1/bar
DelHads 27300 KJ/kmol

Oxygen (Combustion)
kads 7.87E-07 1/bar
DelHads 92800 KJ/kmol

Methane (Reforming)
kads 6.65E-04 1/bar
DelHads 38280 KJ/kmol

CO
kads 8.23E-05 1/bar
DelHads 70650 KJ/kmol

H2
kads 6.12E-09 1/bar
DelHads 82900 kJ/kmol

H2O
kads 1.77E-05 bar
DelHads -88680 kJ/kmol

1st Equation Total Oxidation

From Paper
k1 1st term 2.920E+06 kmol/(kgcat bar^2 h) 8.111E+02
Ea1 1st term 86000 KJ/kmol
 k1 2nd term 2.46E+06 kmol/(kgcat bar^2 h) 6.833E+02
Ea1 2nd term 86000 KJ/kmol

Den1 1.6265

R1-Toxd 1st term 4.4829E-01 kmol / kgcat hr

R1-Toxd 1st term 6.1426E-01 kmol / kgcat hr

2nd Equation SMR to CO

From Paper
k2 4.225E+15 kmol bar^0.5/(kgcat h) 1.174E+12
Ea2 240100 KJ/kmol

ko,eq-SR 1.20E+13 bar^2

Ea 26830 1/K
Ke,2 48.7749
5972554816

2.05E-12
Driving Force 2nd term 5.5356330274E-05 4.88E+11

Den2 1.0928 2321.757779 5.54E-05

2.039456321 553563.3
R2-SMR 2.1527E+03 kmol / kgcat hr
47099.22624
13.0831184
0.049944644
Forward Reaction
k2 4.225E+15 kmol bar^0.5/(kgcat h)
Ea2 240100 KJ/kmol

5.495285E-13
R2-forward 2.3550E+03 kmol/(kgcat h)

Backward Reaction
ko,eq-SR 1.20E+13 bar^2
Ea 26830 1/K

3rd Equation WGS 0.049944644

From Paper
k3 1.020E+15 kmol bar^0.5/(kgcat h)
 Ea3 243900 KJ/kmol

ko,eq-SR 2.12E+11 bar^2

Ea 22430 1/K
Ke,2 63.5795

Driving Force 2nd term 0

Den3 1.0928 24245.43624

6.734843401
R3-WGS 2.7706E+02 kmol / kgcat hr 63.57951327
1.572834E-12

4th Equation SMR to CO2

From Paper
k4 1.955E+06 kmol/(kgcat bar h)
Ea4 67130 KJ/kmol

ko,eq-SMR to CO2 1.77E-02 ---

Ea -4400 1/T
Ke,2 1.3035

Driving Force 2nd term 9.82E+23

Den3 1.0928 2433.474768

6.759652E-11
R4-RWGS 4.4217E+00 kmol / kgcat hr

Dudukovic 2007 LHHW

Forzatti 2009 LHHW corrected
 0.05
0.01
0.3
0.02
0.57
0.05

Adsorption
From Aspen
Methane (Combustion)
A -13.5844 1/Pa
B 3283.62

Oxygen (Combustion)
A -25.5680 1/Pa
B 11161.90

Methane (Reforming)
A -18.8286 1/Pa
B 4604.28

CO
A -20.9181 1/Pa
B 8497.71

H2
A -30.4246 1/Pa
B 9971.13

H2O
A -10.9419 Pa
B -10666.35

From Aspen
Kinetic Term k1 1st term 8.111E-08 kmol/(kgcat Pa^2 s)
Ea1 1st term 86000 KJ/kmol
 k1 2nd term 6.833E-08 kmol/(kgcat Pa^2 s)
Ea1 2nd term 86000 KJ/kmol

Den1 1.6265

R1-Toxd 1st term 4.4829E-01 kmol / kgcat hr

R1-Toxd 1st term 6.1426E-01 kmol / kgcat hr

Checked OK

From Aspen
Kinetic Term k2 3.711E+14 kmol Pa^0.5/(kgcat s)
Ea2 240100 KJ/kmol

ko (paper) 30.1140 From Paper

Ea (paper) -26830 From Paper
Ke,2 48.7749 bar^2 From Paper

A -53.1399
B 26830
Ke,2 (Aspen) 2.0502344545984E-12 Pa^2 From Aspen
Driving Force 2nd term 1.3169225568053E+29

Den2 1.0928
Ke,2
R2-SMR 2.1527E+03 kmol / kgcat hr
((B59*EXP(-B60/($B$1*$B$14)))/B8^2.5)*(B4*B9-B8^3*B6/(B62*EXP(-B63/$B$14)))/B71
((H59*EXP(-H60/($B$1*$B$14)))/C8^2.5)*(C4*C9-C8^3*C6*EXP(H66+H67/$B$14))/H71

Driving force k2 1.174E+12

Ea2 240100
A 2.779E+01 kmol bar^0.5/(kgcat s)
B -28878.9992783257 KJ/kmol

2.3550E+03 kmol/(kgcat h)
2.3550E+03

ko (paper) 30.1140 From Paper

Ea (paper) -26830 From Paper

From Aspen
Kinetic Term k3 8.960E+13 kmol Pa^0.5/(kgcat s)
 Ea3 243900 KJ/kmol

ko (paper) 26.0780 From Paper

Ea (paper) -22430 From Paper
Ke,2 63.5795 bar^2 From Paper

A -49.1039
B 22430
Ke,2 (Aspen) 1.5728336826269E-12 Pa^2 From Aspen
Driving Force 2nd term #VALUE!

Den3 1.0928

R3-WGS 2.7706E+02 kmol / kgcat hr

(B79*EXP(-B80/($B$1*$B$14)))/B8^3.5*(B4*B9^2-B8^4*B7/(B82*EXP(-B83/$B$14)))/B91
(H79*EXP(-H80/($B$1*$B$14)))/C8^3.5*(C4*C9^2-C8^4*C7*EXP(H86+H87/$B$14))/H91

From Aspen
Kinetic Term k4 5.431E-03 kmol/(kgcat Pa s)
Ea4 67130 KJ/kmol

ko (paper) -4.0360 From Paper

Ea (paper) 4400 From Paper
Ke,2 1.3035 bar^2 From Paper

A 4.0360
B -4400
Ke,2 (Aspen) 0.7671482055 Pa^2 From Aspen
Driving Force 2nd term #VALUE!

Den3 1.0928

R4-RWGS 4.4217E+00 kmol / kgcat hr

(B99*EXP(-B100/($B$1*$B$14)))/B8*(B6*B9-B8*B7/(B102*EXP(-B103/$B$14)))/B111
(H99*EXP(-H100/($B$1*$B$14)))/C8*(C6*C9-C8*C7*EXP(H102+H103/$B$14))/H111
*EXP(-B63/$B$14)))/B71
H66+H67/$B$14))/H71
*EXP(-B83/$B$14)))/B91
(H86+H87/$B$14))/H91

B103/$B$14)))/B111
H103/$B$14))/H111
Gas Constant 8.314 KJ/kmol K
Partial pressures
Atm Pa 101325
P-CH4 0.05 5066.25
P-O2 0.01 1013.25
P-CO 0.3 30397.5
P-CO2 0.02 2026.5
P-H2 0.57 57755.25
P-H2O 0.05 5066.25

1 101325

Temperature 750 C
1023 K

Luyben 2016
KoF - SMR 0.1 kmol / m3 s Pa
275000 KJ / kmol

Rf - SMR 2.32967961E-08 kmol / m3 s

KoB - SMR 9.70E-14 kmol / m3 s Pa

47400 KJ / kmol

Rb - SMR 6.46930475E-07 kmol / m3 s

KoF - WGS 2.60E-07 kmol / m3 s Pa

47400 KJ / kmol

Rf - WGS 1.7340404472 kmol / m3 s

KoB - WGS 1.58E-05 kmol / m3 s Pa

85460 KJ / kmol

Rb - WGS 0.0797722263 kmol / m3 s

Anderson 2014
KoF - WGS kmol / m3 s Pa
KJ / kmol

Rf - WGS #VALUE! kmol / m3 s

KoB - WGS kmol / m3 s Pa

KJ / kmol

Rb - WGS #VALUE! kmol / m3 s

Hoang 2004
Ads - CO 8.23E-05 1/bar
-70650 KJ/kmol
K - CO 3.33E-01 1/bar

Ads - H2 6.12E-09 1/bar

-82900 KJ/kmol
K - H2 1.05E-04 1/bar

Ads - CH4 6.65E-04 1/bar

-38280 KJ/kmol
K - CH4 5.99E-02 1/bar

Ads - H2O 1.77E+05 --

88680 KJ/kmol
K - H2O 5.25E+00 --

DEN 1.5632
SMR Rxn for ATR
KoF - SMR 4.23E+15 kmol / kgcat hr bar^0.5
240100 KJ / kmol
K - SMR 2321.757778975

Ke - SMR 5.75E+12 bar^2

-11476
Keq - SMR 7.72E+07

R - SMR 9.68E+00 kmol/kgcat hr

2.69E-03 kmol/kgcat s

WGS Rxn for ATR

KoF - WGS 1.96E+06 kmol / kgcat hr bar^0.5
 67130 KJ / kmol
K - WGS 730.0424304095

Ke - WGS 1.26E-02 bar^2

4639
Keq - WGS 1.17E+00

R - WGS 2.77E+00 kmol/kgcat hr

7.70E-04 kmol/kgcat s
 Duda - Forward Reaction Duda - Forward Reaction
CH4 + H2O -> CO + 3H2 CH4 + 2H2O -> CO2 + 4H2
4.225e15*exp(-240100/RT) 1.02e15*exp(-243900/RT)
4.22E+15 1.02E+15
R 8.314 240100 243900
Temp
600 5.272E-06 5.949E-07
700 5.107E-03 6.425E-04
800 8.868E-01 1.211E-01
900 4.895E+01 7.120E+00
1000 1.211E+03 1.854E+02
1100 1.673E+04 2.669E+03
1200 1.492E+05 2.463E+04
1300 9.498E+05 1.615E+05
 Duda Duda - Forward Reaction Duda Nezhad - Forward Reaction
Relative Rate CO + H2O -> CO2 + H2 Relative Rate CH4 + H2O -> CO + 3H2
CO / CO2 1.955e6*exp(-67130/RT) WGS/SMR CO 5.852e17*exp(-204000/RT)
from SMR 1.96E+06 5.85E+17
67130 204000

0.1128 2.797E+00 5.306E+05 1.016E+00

0.1258 1.913E+01 3.745E+03 3.500E+02
0.1365 8.088E+01 9.121E+01 2.799E+04
0.1455 2.482E+02 5.071E+00 8.453E+05
0.1530 6.088E+02 5.026E-01 1.291E+07
0.1595 1.269E+03 7.582E-02 1.202E+08
0.1651 2.339E+03 1.568E-02 7.711E+08
0.1701 3.924E+03 4.131E-03 3.717E+09
Nezhad - Forward Reaction Nezhad Duda - Forward Reaction Duda
CH4 + 2H2O -> CO2 + 4H2 Relative Rate CO + H2O -> CO2 + H2 Relative Rate
1.02e15*exp(-243900/RT) CO / CO2 1.955e6*exp(-67130/RT) WGS/SMR CO
1.02E+15 from SMR 1.96E+06
243900 67130

5.949E-07 5.856E-07 2.797E+00 2.753E+00

6.425E-04 1.836E-06 1.913E+01 5.465E-02
1.211E-01 4.325E-06 8.088E+01 2.890E-03
7.120E+00 8.423E-06 2.482E+02 2.937E-04
1.854E+02 1.436E-05 6.088E+02 4.715E-05
2.669E+03 2.221E-05 1.269E+03 1.056E-05
2.463E+04 3.195E-05 2.339E+03 3.033E-06
1.615E+05 4.345E-05 3.924E+03 1.056E-06
Gas Constant 8.314 KJ/kmol K
Partial pressures
Bar Pa 100000
P-CH4 0.2 20000
P-O2 0.05 5000
P-CO 0.1 10000
P-CO2 0.1 10000
P-H2 0.3 30000
P-H2O 0.25 25000

1 100000

Temperature 750 C
1023 K

Adsorption
From Paper
Methane (Combustion)
kads 1.26E-01 1/bar
DelHads 27300 KJ/kmol

Oxygen (Combustion)
kads 7.87E-07 1/bar
DelHads 92800 KJ/kmol

Methane (Reforming)
kads 6.65E-04 1/bar
DelHads 38280 KJ/kmol

CO
kads 8.23E-05 1/bar
DelHads 70650 KJ/kmol

H2
kads 6.12E-09 1/bar
DelHads 82900 kJ/kmol

H2O
kads 1.77E+05 bar
DelHads -88680 kJ/kmol
From Paper

Keq2 -26830 30.114

Keq3 -22430 26.078
Keq4 4400 -4.036

From Paper
 kmol/kgcat h
k1A 2.96E+06 86000
K1B 2.46E+06 86000
k2 4.23E+15 240100
k3 1.02E+15 243900
k4 1.96E+06 67130
 0.05
0.01
0.3
0.02
0.57
0.05

Adsorption
From Aspen
Methane (Combustion)
A -2.0715 1/bar
B 3283.62 KJ/kmol

Oxygen (Combustion)
A -14.0550 1/bar
B 11161.90 KJ/kmol

Methane (Reforming)
A -7.3157 1/bar
B 4604.28 KJ/kmol

CO
A -9.4051 1/bar
B 8497.71 KJ/kmol

H2
A -18.9117 1/bar
B 9971.13 kJ/kmol

H2O
A 12.0839 bar
B -10666.35 kJ/kmol
For Aspen
A B
-30.114 26830
-26.078 22430
4.036 -4400

For Aspen
kmol/kgcat s
822.22 86000
683.33 86000
1.17E+12 240100
2.83E+11 243900
543.06 67130
Gas Constant 8.314 KJ/kmol K
Partial pressures
Bar Pa 100000
P-CH4 0.2 20000 0.05
P-O2 0.05 5000 0.01
P-CO 0.1 10000 0.3
P-CO2 0.1 10000 0.02
P-H2 0.3 30000 0.57
P-H2O 0.25 25000 0.05

1 100000

Temperature 750 C
1023 K

Adsorption Adsorption
From Paper From Aspen
Methane (Combustion) Methane (Combustion)
kads 4.02E+05 1/bar A 12.9042
DelHads 103500 KJ/kmol B -12448.88

Oxygen (Combustion) Oxygen (Combustion)

kads 5.08E+04 1/bar A 10.8357
DelHads 66200 KJ/kmol B -7962.47

Methane (Reforming) Methane (Reforming)

kads 6.65E-04 1/bar A -7.3157
DelHads -38280 KJ/kmol B 4604.28

CO CO
kads 8.23E-05 1/bar A -9.4051
DelHads -70650 KJ/kmol B 8497.71

H2 H2
kads 6.12E-09 1/bar A -18.9117
DelHads -82900 kJ/kmol B 9971.13

H2O H2O
kads 1.77E+05 bar A 12.0839
DelHads 88680 kJ/kmol B -10666.35

From Paper For Aspen

A B
Keq2 5.75E+12 -11476 -29.3802 11476
Keq3 7.24E+10 -21646 -25.0055 21646
Keq4 1.26E-02 4639 4.3741 -4639
Wu CO2 reform
Keq5 42.97 -30782 -42.97 30782

From Paper For Aspen

kmol/kgcat h kmol/kgcat s
k1 5.852E+17 204000 1.626E+14 204000
k2 4.225E+15 240100 1.174E+12 240100
k3 1.020E+15 243900 2.833E+11 243900
k4 1.955E+06 67130 543.06 67130

Wu CO2 reform
k5 8.71E-02 23700 2.419E-05 23700
1/bar
KJ/kmol

1/bar
KJ/kmol

1/bar
KJ/kmol

1/bar
KJ/kmol

1/bar
kJ/kmol

bar
kJ/kmol
Reaction 3 and 4 interchanged
from original paper in this table

Reaction 3 and 4 interchanged

from original paper in this table