Mass and Energy Blance

CHEN5020

Group 6
Student Name Student ID
Rachel Taylor 19777144
Reza Tashakori Jahromi 21254406
Lyurongxin Tang 21660207
Elliott Pieters 21731080
Assignment 1&2
1. Desulphurization unit

1. Pressure 3MPa
2. Catalyst Activated Carbon/Zinc oxide
3. Reactants N/A
4. Products N/A
5. Conversion N/A
2. Steam Methane Primary Reforming
1. Pressure 3MPa
2. Temperature 800 K
3. CatalystNi/Al oxides
4. Reactants CH4 + H2O
5. Products CO + 3H2
6. Reaction CH4 + H2O -> CO + 3H2
7. Conversion 66 %
3. Steam Methane Secondary Reforming
1. Pressure 3MPa
2. Temperature 1300 K
3. CatalystNi
4. Reactants 2CH4 + O2
5. Products 2CO + 4H2
6. Reaction 2CH4 + O2 -> 2CO + 4H2
7. Conversion high 97% with 17%CO
4. High Temperature Shift Reactor
1. Pressure 3.4MPa
2. Temperature 700K
3. CatalystFe/Cr (Ferrochrome catalysts)
4. Reactants CO + H2O
5. Products CO2 + H2
6. Reaction CO + H2O -> CO2 + H2
7. Conversion Up to 78% conversion
5. Low Temperature Shift Reactor
1. Pressure 2.1MPa
2. Temperature 500K
3. CatalystCatalyst: Cu/Zn/Al
4. Reactants CO + H2O
5. Products CO2 + H2
6. Reaction CO + H2O -> CO2 + H2
7. Conversion Up to 91% conversion
6. CO2 removal
1. Pressure 0.4MPa Up to 3MPa
2. Temperature 300 to 360 K
3. Solvent aMDEA
4. Reactants N/A
5. Products N/A
6. Conversion Removal 95% CO2
7. Methanation
1. Pressure 3 MPa
2. Temperature 900 K
3. CatalystNi
4. Reactants CO + 3H2, CO2 + 4H2
 5. Products CH4 + H2O
6. Reaction CO + 3H2 -> CH4 + H2O
CO2 + 4H2 -> CH4 + 2H2O
7. Conversion 98%
8. Haber-Bosch Reactor
a. Pressure 20 MPa
b. Temperature 700 K
c. Catalyst Fe oxide (wustite)
d. Reactants 3H2 + N2
e. Products NH3
f. Reaction 3H2 + N2 -> NH3
g. Conversion SP 18%, OA 98%
9. Condenser
1. Pressure N/A
2. Temperature 240 K
3. CatalystN/A
4. Reactants N/A
5. Products N/A
6. Conversion N/A

Reference:
[1] Appl M, Ammonia, 3. Production Plants. Ullmann’s Encyclopedia of Industrial Chemistry, 2000.

[2] Oni, A.O. ; Giwa, T. ; Font-Palma, C. ; Fadare, D.A. Comparative Techno-Economic and Life Cycle
Greenhouse Gas Assessment of Ammonia Production from Thermal Decomposition of Methane and
Steam Methane Reforming Technologies. (2023). International Journal of Greenhouse Gas Control,
Vol.123, 103819. https://doi.org/https://doi.org/10.1016/j.ijggc.2022.103819
[3] Nosherwani, Shahmir Ali ; Neto, Rui Costa. Techno-Economic Assessment of Commercial
Ammonia Synthesis Methods in Coastal Areas of Germany. (n.d.). Journal of Energy Storage. 2021,
Vol.34, p.102201, Article 102201. https://doi.org/https://doi.org/10.1016/j.est.2020.102201.

[4] Heiser, Daniel, author. Conversion of Ammonia Plants to Methanol Production. (1982). Ann
Arbor, Mich. : Standards Development and Support Branch, Emission Control Technology Division,
Office of Mobile Source Air Pollution Control, Office of Air, Noise and Radiation, U.S. Environmental
Protection Agency.
Assignment 3&4
Steam Methane Reformer Primary

CH4 + H2O ► CO + 3H2

Assume: SP conv. = 0.66, H2O 40 % excess, pure methane

In Out
Species CH4 H2O H2 CO CH4 H2O
Stoichiometri
c 1 1 3 1
kg/h 57016 59159 14186 65701 19386 16903
kgmol/h 3554 3284 7037 2346 1208 938
mol fraction 0.26 0.24 0.51 0.52 0.27 0.21

57016 kg/h CH4 @ 0.716 kg/Nm3 = 79654 Nm3/h CH4

Nm3 conditions for CH4 are 273.15 K, 101325 Pa, 8314, 1m3, CH4 = 16.043 kg/kgmol

PV =nRT
101325 ×1
n=
8314 ×273.15
0.044618 ×16.043=0.716 kg /m3
Steam Methane Reformer Secondary

2CH4 + O2 ► 2CO + 4H2

Assume: SP conv. = 0.97, O2 in excess added by air, air mol fraction 0.21 O2 0.79 N2

In Out
Species CO (from SMR1) CH4 O2 N2 H2 CO N2
Stoichiometri
c 2 1 4 2
kg/h 65701 19386 48556 159919 4726 98531 159919
kgmol/h 2346 1208 1517 5709 2344 3518 5709
mol fraction 0.22 0.11 0.14 0.53 0.20 0.30 0.49

Shift Conversion HTS

CO + H2O ► CO2 + H2
Assume: SP conv. = 0.78, H2O 40 % excess, O2 purged

In Out
Species N2 CO H2O N2 CO2 H2 CO
Stoichiometri
c 1 1 1 1
kg/h 159919 0 0 159919 38433 145632 21677
kgmol/h 5709 3518 3841 5709 2744 12125 774
 mol fraction 0.44 0.27 0.29 0.27 0.13 0.57 0.04
Shift Conversion LTS

CO + H2O ► CO2 + H2
Assume: SP conv. = 0.91, H2O 40 % excess

In Out
Species N2 CO H2O N2 CO2 H2 CO
Stoichiometric 1 1 1 1
kg/h 159919 21677 17762 159919 30993 25863 1951
kgmol/h 5709 774 986 5709 704 12829 70
mol fraction 0.76 0.10 0.13 0.30 0.04 0.66 0.00

CO2 removal via solvent

Physical removal
Assume: SP removal = 0.99, all other compounds pass through completely

In Out
Species CO2 CO2 (out) CO2 (retained)
Stoichiometric
kg/h 151746 150228 1517
kgmol/h 3448 3414 34.48

Methanation

CO + 3H2 ► CH4 + H2O

CO2 + 4H2 ► CH4 + H2O
Assume: SP conv. = 1.0, all components other than H2 and N2 removed here

In Out
Species N2 CO CO2 H2 N2 H2 CH4 H2O
Stoichiometric
CO2 1 3 1 1
Stoichiometric
CO2 1 4 1 2
kg/h 159919 1951 1517 25863 159919 25164 1671 2497
12482.2 104.1 138.6
kgmol/h 5709 69.65 34.48 12829.12 5709 4 3 1
mol fraction 0.31 0.00 0.00 0.69 0.31 0.68 0.01 0.01

Haber-Bosch Reactor

3H2 + N2 ► 2NH3
Assume SP conv. 0.18, OA conv. 0.98, assume N2 40 % excess

Overall excluding recycle:

In out
Species N2 H2 NH3 N2 H2
Stoichiometric 1.00 3.00 2.00
 kg/h 159919.17 25164.20 138888.89 45691.19 503.28
kgmol/h 5708.54 12482.24 8155.06 1631.01 249.64
mol fraction 0.31 0.69 0.81 0.16 0.02
Annual tonnes NH3 OSD tonne/day NH3 tonne/h NH3 kg/hr NH3
1000000 300 3333.33 138.89 138889

With Recycle, assuming no NH3 in stream and 0.18 SP conv:

Recycle H2 N2 total
kgmol/h 55476 25889 81365
kg/hr 111840 725250 837090
mol fraction 0.68 0.32 1.00
Fresh Feed H2 N2 total
kgmol/h 12482 5709 18191
kg/hr 25164 159919 185083
mol fraction 0.69 0.31 1.00
Total HB reactor flow (single
pass)
H2 N2 total
kgmol/h 67958 31597 99556
kg/hr 137004 885169 1022173
fraction 0.68 0.32 1.00

In out
Species N2 H2 NH3 N2 H2
Stoichiometric 1.00 3.00 2.00
kg/h 885169.24 137004.00 138887.81 770942.15 112343.28
kgmol/h 31597 67958 8155 27520 55726
mol fraction 0.32 0.68 0.09 0.30 0.61

CO2 Emissions

Direct CO2 emissions from CH4: 3554 kgmol CH4 converted to 3554 kgmol CO2

kg kgmol
mass flow CO 2 = ×44.009
h h
kg kg
mass flow CO 2 =156406.5
h h
kg
CO 2
h 156401 kgCO 2
= =1.13
kg 138889 kgNH 3
NH 3
h
Indirect emissions (Source: https://pubs.rsc.org/en/content/articlehtml/2020/ee/c9ee02873k)

Emitter kgCO2/kgNH3

CH4 extraction 0.07

Steam to turbine (power) 0.17

Steam to SMR 0.10

Other steam 0.03

Heat loss/other 0.17

Total 0.54

Therefore

1.13 + 0.54 = 1.67 kgCO2/kgNH3

Extent of reaction:

n i−ni 0
ξ H 2=
vi
55726−67958
ξ H 2= =4078
−3
ξH2 55726 67958 4078
-3

ξNH3 8155 0 4078

2

ξN2 27520 31597 4078

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