Natural Gas Pyrolysis (NGP)

- Chemical Reactions

0
𝐶𝐻4 ↔ 𝐶 + 2𝐻2 , ∆𝐻298 = +74,87 𝑘𝐽/𝑚𝑜𝑙
- Kinetic

𝑃𝐻22
𝑘𝐾𝐶𝐻4 (𝑃𝐶𝐻4 − )
𝐾𝑃
𝑟= (S1)
1 1.5 2
(1 + 𝐾𝐶𝐻4 𝑃𝐶𝐻4 + 𝑃 )
𝐾𝐻2 𝐻2

Dry Reforming of Methane (DMR)

- Chemical Reactions
0
1) 𝐶𝐻4 + 𝐶𝑂2 ↔ 2𝐶𝑂 + 2𝐻2 , ∆𝐻298 = +247𝑘𝐽/𝑚𝑜𝑙
0
2) 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +41.7𝑘𝐽/𝑚𝑜𝑙
0
3) 𝐶𝐻4 ↔ 𝐶 + 2𝐻2 , ∆𝐻298 = +74,87 𝑘𝐽/𝑚𝑜𝑙
- Kinetic
2
𝑘1 𝑃𝐶𝐻4 𝑃𝐶𝑂2 (𝑃𝐶𝑂 𝑃𝐻2 )
𝑟1 = (1 − ) (S2)
(𝐾𝐶𝑂2 ,1 𝑃𝐶𝑂2 + 𝐾𝐶𝐻4,1 𝑃𝐶𝐻4 ) 𝐾𝑃1 (𝑃𝐶𝐻4 𝑃𝐶𝑂2 )
𝑘2 𝐾𝐶𝑂2 ,2 𝐾𝐻2,2 𝑃𝐶𝑂2 𝑃𝐻2 (𝑃𝐶𝑂 𝑃𝐻2𝑂 )
𝑟2 = 2 (1 − ) (S3)
(1 + 𝐾𝐶𝑂2 ,2 𝑃𝐶𝑂2 + 𝐾𝐻2,2 𝑃𝐻2 ) 𝐾𝑃2 (𝑃𝐶𝑂2 𝑃𝐻2 )

𝑃𝐻22
𝑘3 𝐾𝐶𝐻4,3 (𝑃𝐶𝐻4 − )
𝐾𝑃3
𝑟3 = 2
(S4)
1
(1 + 𝐾𝐶𝐻4,3 𝑃𝐶𝐻4 + 𝑃𝐻1.5 )
𝐾𝐻2,3 2

Steam Reforming of Methane (SMR)

- Chemical Reactions
0
1) 𝐶𝐻4 + 𝐻2 𝑂 ↔ 3𝐻2 + 𝐶𝑂, ∆𝐻298 = +206 𝑘𝐽/𝑚𝑜𝑙
0
2) 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +41.7𝑘𝐽/𝑚𝑜𝑙
0
3) 𝐶𝐻4 + 2𝐻2 𝑂 ↔ 4𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +253.1 𝑘𝐽/𝑚𝑜𝑙
- Kinetic

𝑘1 𝑃𝐻32 𝑃𝐶𝑂
2.5 (𝑃𝐶𝐻4 𝑃𝐻2 𝑂 − 𝐾1
)
𝑃𝐻2 (S5)
𝑟1 =
𝐷𝐸𝑁 2

𝑘2 𝑃𝐻 𝑃𝐶𝑂
(𝑃 𝑃 − 2 2)
𝑃𝐻2 𝐶𝑂 𝐻2𝑂 𝐾2 (S6)
𝑟2 = 2
𝐷𝐸𝑁

𝑘3 2
𝑃𝐻42 𝑃𝐶𝑂2
(𝑃 𝑃
𝐶𝐻4 𝐻2 𝑂 − )
𝑃𝐻3.5
2
𝐾3 (S7)
𝑟3 =
𝐷𝐸𝑁 2

Entropy 2020, 22, x; doi: FOR PEER REVIEW www.mdpi.com/journal/entropy

Entropy 2020, 22, x FOR PEER REVIEW 2 of 7

𝐾𝐻2𝑂 𝑃𝐻2𝑂
𝐷𝐸𝑁 = 1 + 𝐾𝐶𝐻4 𝑃𝐶𝐻4 + 𝐾𝐶𝑂 𝑃𝐶𝑂 + 𝐾𝐻2 𝑃𝐻2 + (S8)
𝑃𝐻2

Partial Oxidation of Methane (POM)

- Chemical Reactions
0
1) 𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂, ∆𝐻298 = −802 𝑘𝐽/𝑚𝑜𝑙
0
2) 𝐶𝐻4 + 𝐻2 𝑂 ↔ 3𝐻2 + 𝐶𝑂, ∆𝐻298 = +206 𝑘𝐽/𝑚𝑜𝑙
0
3) 𝐶𝐻4 + 𝐶𝑂2 ↔ 2𝐶𝑂 + 2𝐻2 , ∆𝐻298 = +247𝑘𝐽/𝑚𝑜𝑙

- Kinetic

(𝑘1 𝑃𝐶𝐻4 𝑃𝑂22 )

𝑟1 = 2 (S9)
(1 + 𝐾𝐶𝐻4 𝑃𝐶𝐻4 + 𝐾𝑂2 )
3
𝑃𝐻2 𝑃𝐶𝑂
𝑟2 = 𝑘2 𝑃𝐶𝐻4 𝑃𝐻2𝑂 (1 − ) (S10)
𝐾2 𝑃𝐶𝐻4 𝑃𝐻2𝑂
𝑃𝐻22 𝑃𝐶𝑂
2
𝑟3 = 𝑘3 𝑃𝐶𝐻4 𝑃𝐶𝑂2 (1 − ) (S11)
𝐾3 𝑃𝐶𝐻4 𝑃𝐶𝑂2

Water Electrolysis (WE)

- Chemical Reactions
𝐻2 𝑂 → 1/2𝑂2 + 2𝐻2

Coal Gasification (CG)

- Chemical Reactions
0
1) 𝐶 + 𝐶𝑂2 ↔ 2𝐶𝑂, ∆𝐻298 = −542.1 𝑘𝐽/𝑚𝑜𝑙
0
2) C + H2 O ↔ CO + H2 , ∆H298 = -583.3 kJ/mol
0
3) 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +41.7𝑘𝐽/𝑚𝑜𝑙
- Kinetic
0.31
𝑟1 = 𝑘1 𝑃𝐶𝑂 2 (S12)
𝑟2 = 𝑘2 𝑃𝐻0.73
2𝑂 (S13)

𝑘3 𝑃𝐻 𝑃𝐶𝑂
(𝑃 𝑃 − 2 2)
𝑃𝐻2 𝐶𝑂 𝐻2𝑂 𝐾3
𝑟3 = 2 (S14)
𝐾𝐻2𝑂 𝑃𝐻2𝑂
(1 + + 𝐾𝐻2 𝑃𝐻2 + 𝐾𝐶𝑂 𝑃𝐶𝑂 )
𝑃𝐻2

Autothermal Reforming of Methane (ATR)

- Chemical Reactions
0
1) 𝐶𝐻4 + 𝐻2 𝑂 ↔ 3𝐻2 + 𝐶𝑂, ∆𝐻298 = +206 𝑘𝐽/𝑚𝑜𝑙
0
2) 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +41.7𝑘𝐽/𝑚𝑜𝑙
0
3) 𝐶𝐻4 + 2𝐻2 𝑂 ↔ 4𝐻2 + 𝐶𝑂2 , ∆𝐻298 = +253.1 𝑘𝐽/𝑚𝑜𝑙
0
4) 𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂, ∆𝐻298 = −802 𝑘𝐽/𝑚𝑜𝑙
- Kinetic
Entropy 2020, 22, x FOR PEER REVIEW 3 of 7

𝑘1 𝑃𝐻32 𝑃𝐶𝑂
2.5 (𝑃𝐶𝐻4 𝑃𝐻2 𝑂 − 𝐾1
)
𝑃𝐻2 (S15)
𝑟1 =
𝐷𝐸𝑁 2

𝑘2 𝑃𝐻 𝑃𝐶𝑂
(𝑃 𝑃 − 2 2)
𝑃𝐻2 𝐶𝑂 𝐻2𝑂 𝐾2 (S16)
𝑟2 = 2
𝐷𝐸𝑁

𝑘3 2
𝑃𝐻42 𝑃𝐶𝑂2
(𝑃𝐶𝐻 𝑃𝐻 𝑂 − )
𝑃𝐻3.5
2
4 2 𝐾3 (S17)
𝑟3 =
𝐷𝐸𝑁 2
(𝑘4 𝑃𝐶𝐻4 𝑃𝑂22 )
𝑟4 = 2 (S18)
(1 + 𝐾𝐶𝐻4,4 𝑃𝐶𝐻4 + 𝐾𝑂2 )
𝐾𝐻2𝑂 𝑃𝐻2𝑂
𝐷𝐸𝑁 = 1 + 𝐾𝐶𝐻4 𝑃𝐶𝐻4 + 𝐾𝐶𝑂 𝑃𝐶𝑂 + 𝐾𝐻2 𝑃𝐻2 + (S19)
𝑃𝐻2

Table S1. Thermodynamic and rate constants. Constants are in [mol, kg, s, bar].
Natural Gas Pyrolysis [1]
Parameter Value Parameter Value
58893 567
𝑘 6.95 · 103 exp (− ) 𝐾𝐶𝐻4 0.21 exp (− )
𝑅𝑇 𝑅𝑇

133210 84400
𝐾𝐻2 5.18 · 107 exp (− ) 𝐾𝑃 2.98 · 105 exp (− )
𝑅𝑇 𝑅𝑇
Dry Reforming of Methane [1]
Parameter Value Parameter Value
3115.22 81030
𝑘1 1.35 · 10−8 exp (− ) 𝑘2 0.35 · 106 exp (− )
𝑅𝑇 𝑅𝑇

58893 4883.32
𝑘3 6.95 · 103 exp (− ) 𝐾𝐶𝑂2,1 9.25 · 10−8 exp (+ )
𝑅𝑇 𝑅𝑇

4606.68 9262
𝐾𝐶𝐻4,1 2.46 · 10−7 exp (+ ) 𝐾𝐶𝑂2,2 0.5771 exp (+ )
𝑇 𝑅𝑇

6025 567
𝐾𝐻2,2 1.494 exp (+ ) 𝐾𝐶𝐻4,3 0.21 exp (− )
𝑅𝑇 𝑅𝑇

133210 259660
𝐾𝐻2,3 5.18 · 107 exp (− ) 𝐾𝑃1 6.78 · 1014 exp (− )
𝑅𝑇 𝑅𝑇

36580 84400
𝐾𝑃2 56.4971 exp (− ) 𝐾𝑃3 2.98 · 105 exp (− )
𝑅𝑇 𝑅𝑇
Steam Reforming of Methane [2]
Parameter Value Parameter Value
240100 67130
𝑘1 4.22 · 1015 exp (− ) 𝑘2 1.96 · 106 exp (− )
𝑅𝑇 𝑅𝑇

243900 38280
𝑘3 1.02 · 1015 exp (− ) 𝐾𝐶𝐻4 6.65 · 10−4 exp (+ )
𝑅𝑇 𝑅𝑇

88680 82900
𝐾𝐻2𝑂 1.77 · 105 exp (− ) 𝐾𝐻2 6.12 · 10−9 exp (+ )
𝑅𝑇 𝑅𝑇
Entropy 2020, 22, x FOR PEER REVIEW 4 of 7

70650 27106
𝐾𝐶𝑂 8.23 · 10−5 exp (+ ) 𝐾1 exp (30.42 − )
𝑅𝑇 𝑇

4160 31266
𝐾2 exp (−3.798 + ) 𝐾3 exp (34.218 − )
𝑇 𝑇
Partial Oxidation of Methane [3,4]
Parameter Value Parameter Value
166000 29000
𝑘1 1.10 exp (+ ) 𝑘2 4.19 · 10−9 exp (+ )
𝑅𝑇 𝑅𝑇

23700 103500
𝑘3 2.42 · 10−9 exp (+ ) 𝐾𝐶𝐻4 6.65 · 10−4 exp (+ )
𝑅𝑇 𝑅𝑇

66200 95411
𝐾𝑂 2 1.77 · 10−5 exp (+ ) 𝐾2 5.75 · 1012 exp (− )
𝑅𝑇 𝑅𝑇

179960
𝐾3 7.24 · 1010 exp (− )
𝑅𝑇
Coal Gasification [5,6]
Parameter Value Parameter Value
220000 245000
𝑘1 2.07 · 107 exp (− ) 𝑘2 1.12 · 108 exp (− )
𝑅𝑇 𝑅𝑇

67130 88680
𝑘3 1.96 · 106 exp (− ) 𝐾𝐻2𝑂 1.77 · 105 exp (− )
𝑅𝑇 𝑅𝑇

82900 70650
𝐾𝐻2 6.12 · 10−9 exp (+ ) 𝐾𝐶𝑂 8.23 · 10−5 exp (+ )
𝑅𝑇 𝑅𝑇

4160
𝐾3 exp (−3.798 + )
𝑇

Auto-thermal Reforming of Methane [7]

Parameter Value Parameter Value
67130 243900
𝑘1 1.955 · 106 exp (− ) 𝑘2 1.02 · 1015 exp (− )
𝑅𝑇 𝑅𝑇

204000 166000
𝑘3 5.852 · 1017 exp (− ) 𝑘4 1.10 exp (+ )
𝑅𝑇 𝑅𝑇

38280 70650
𝐾𝐶𝐻4 6.65 · 10−4 exp (+ ) 𝐾𝐶𝑂 8.23 · 10−5 exp (+ )
𝑅𝑇 𝑅𝑇

82900 88680
𝐾𝐻2 6.12 · 10−9 exp (+ ) 𝐾𝐻2𝑂 1.77 · 105 exp (− )
𝑅𝑇 𝑅𝑇

103500 66200
𝐾𝐶𝐻4,4 6.65 · 10−4 exp (+ ) 𝐾𝑂 2 1.77 · 10−5 exp (+ )
𝑅𝑇 𝑅𝑇

11476 4639
𝐾1 5.75 · 1012 exp (− ) 𝐾2 1.26 · 10−2 exp (+ )
𝑅𝑇 𝑅𝑇

21646
𝐾3 7.242 · 1010 exp (− )
𝑅𝑇
Entropy 2020, 22, x FOR PEER REVIEW 5 of 7

Figure S1. Simulation for Natural Gas Pyrolysis in DWSIM.

Figure S2. Simulation for Dry Reforming of Methane in DWSIM.

Figure S3. Simulation for Steam Reforming of Methane in DWSIM.

Entropy 2020, 22, x FOR PEER REVIEW 6 of 7

Figure S4. Simulation for Partial Oxidation of Methane in DWSIM.

Figure S5. Simulation for Water Electrolysis in DWSIM.

Figure S6. Simulation for Coal Gasification in DWSIM.

Entropy 2020, 22, x FOR PEER REVIEW 7 of 7

Figure S7. Simulation for Auto-thermal Reforming of Methane in DWSIM.

1. Benguerba, Y.; Virginie, M.; Dumas, C.; Ernst, B. Methane dry reforming over Ni-Co/Al2O3:
Kinetic modelling in a catalytic fixed-bed reactor. Int. J. Chem. React. Eng. 2017, 15.
2. Keith, J.M. Hydrogen Education Curriculum Path at Michigan Technological University. 2010.
3. Hoang, D.L.; Chan, S.H.; Ding, O.L. Kinetic modelling of partial oxidation of methane in an
oxygen permeable membrane reactor. Chem. Eng. Res. Des. 2005, 83, 177–186.
4. Fernandes, F.A.N.; Sousa, J.F.; Souza, C.P.; Rodrigues, S. Modeling of partial oxidation of methane
in a membrane reactor; 2005;
5. Umeki, K.; Yamamoto, K.; Namioka, T.; Yoshikawa, K. High temperature steam-only
gasification of woody biomass. Appl. Energy 2010, 87, 791–798.
6. Solli, K.-A.; Kumar Thapa, R.; Moldestad, B.M.E. Screening of Kinetic Rate Equations for
Gasification Simulation Models. Proc. 9th EUROSIM Congr. Model. Simulation, EUROSIM 2016,
57th SIMS Conf. Simul. Model. SIMS 2016 2018, 142, 105–112.
7. Zahedi nezhad, M.; Rowshanzamir, S.; Eikani, M.H. Autothermal reforming of methane to
synthesis gas: Modeling and simulation. Int. J. Hydrogen Energy 2009, 34, 1292–1300.

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