Production of Sustainable

Aviation Fuel from

Renewable CO2

Tufail Ahmed Kaladia

MSc Thesis Defense
30/08/2023
Agenda • Background
• Research objective
• Available literature
• Aspen Plus simulation
• Heat integration
• Economic evaluation
• Conclusion
• Recommendations

2
 Background
Why Sustainable Aviation Fuel (SAF)?

• Aviation accounts for approximately

10% of the global energy needs for
transportation section [1]

• Aviation accounts for approximately

5% of the total human-generated
climate impact [2]

• Dutch government wants to ensure a

minimum of 14% of the aviation fuel
bunkered in Netherlands in 2030 to be
derived from sustainable sources [3]
Figure 1. Sustainable aviation fuel as a strategy to reduce aviation CO2 emissions [2]

3
 Background
Any alternatives?

• Electrification of commercial aviation is

unlikely to happen before 2040 [4]

• Technology Readiness Level (TRL) of

hydrogen fuel cells limits its applicability
in the aviation sector [4]

Figure 2. Alternative strategies to reduce aviation CO2 emissions [5]

4
Research
objective

5
Research methodology

Process
Literature Process Process Economic
Route
Review Simulation Optimization Evaluation
Selection

6
Available literature

Figure 3. Jet fuel production via Fischer-Tropsch pathway [2] Figure 4. Jet fuel production via methanol pathway [2]

7
 Available literature
Methanol-to-Jet (MtJ) pathway

MeOH Jet fuel

Olefin Olefin
Olefin synthesis
oligomerization hydrogenation

8
 Available literature
Olefin synthesis step

Small-pore catalysts Medium-pore catalysts

Number of zeolite
8 10
oxygen atoms/rings

Erionite,
Zeolite T,
Chabazite, ZSM-5,
Typical catalysts
ZK-5, Modified ZSM-5
ZSM-34,
SAPO-34

Typical yields, wt% hydrocarbons

C2= 25 – 55 5 – 25
C3= 20 – 50 20 – 40
Total olefins 50 – 95 50 – 80
C5+ 1 – 15 25 – 60
Coke 0.5 – 5 < 0.5

Table 1. Typical catalysts for olefin synthesis from methanol [6] Figure 5. Reaction kinetics in olefin synthesis step [7]

9
 Available literature
Olefin synthesis step

UOP MTO DMTO / DMTO – II S-MTO MTP Mobil MTO

Temperature 340 – 540 °C 400 – 500 °C 400 – 500 °C 400 – 450 °C 400 – 500 °C
Pressure 1 – 3 bar 1 – 3 bar 1 – 3 bar 1.3 – 1.6 bar 1 – 3 bar
Novel patented version of
Catalyst SAPO-34 SAPO-34 ZSM-5 ZSM-5
SAPO-34

Methanol Conversion 100% 100% 100% 100% 100%

Highly selective towards
Highly selective towards Highly selective towards Highly selective towards Very highly selective towards
Product Selectivity propene, butene and
ethene and propene ethene and propene ethene and propene propene
pentene
Reactor type Fluidized bed Fluidized bed Fluidized bed Fixed bed Fluidized bed
Cracking of higher
Yes No No No No
hydrocarbons
Recycle of cracked / higher
No No No Yes No
hydrocarbons
Recycle of C3- hydrocarbons No No No Yes No
Need of a pre-reactor to
achieve equilibrium of
No No No Yes No
methanol and dimethyl
ether
Composition of reactor
outlet stream available in Yes Yes No Yes Yes
scientific literature

Table 2. Comparison of major Methanol-to-Olefins processes

For references of the values in Table 2, please refer to the thesis report 10
 Available literature
Olefin oligomerization step

Mobil Olefins to Gasoline and Conversion of Olefins to

Distillate (MOGD) process Distillate (COD) process

190 – 310 oC
150 – 360 oC
Temperature 200 – 300 oC
< 280 oC
200 – 280 oC

40 – 100 bar
Pressure 30 – 100 bar 55 bar
10 – 50 bar

0.5 – 1
WHSV 0.2 – 6 h-1
0.1 – 5 h-1

ZSM-5 Zeolite (COD-9)

Catalyst
HZSM-5 HZSM-5

Reactor type Fixed bed Fixed bed

Table 3. Summary of commercially available olefin oligomerization processes Figure 6. Reaction scheme for oligomerization of short-chain olefins [8]

For references of the values in Table 3, please refer to the thesis report 11
 Available literature
Olefin synthesis step

UOP MTO DMTO / DMTO – II S-MTO MTP Mobil MTO

Temperature 340 – 540 °C 400 – 500 °C 400 – 500 °C 400 – 450 °C 400 – 500 °C
Pressure 1 – 3 bar 1 – 3 bar 1 – 3 bar 1.3 – 1.6 bar 1 – 3 bar
Novel patented version of
Catalyst SAPO-34 SAPO-34 ZSM-5 ZSM-5
SAPO-34

Methanol Conversion 100% 100% 100% 100% 100%

Highly selective towards
Highly selective towards Highly selective towards Highly selective towards Very highly selective towards
Product Selectivity propene, butene and
ethene and propene ethene and propene ethene and propene propene
pentene
Reactor type Fluidized bed Fluidized bed Fluidized bed Fixed bed Fluidized bed
Cracking of higher
Yes No No No No
hydrocarbons
Recycle of cracked / higher
No No No Yes No
hydrocarbons
Recycle of C3- hydrocarbons No No No Yes No
Need of a pre-reactor to
achieve equilibrium of
No No No Yes No
methanol and dimethyl
ether
Composition of reactor
outlet stream available in Yes Yes No Yes Yes
scientific literature

Table 2. Comparison of major Methanol-to-Olefins processes

For references of the values in Table 2, please refer to the thesis report 12
 Available literature
Olefins hydrogenation step

Co-Mo/Al2O3 Pt/Al2O3

150 °C
350 °C
Temperature 185 °C
270 – 340 °C
200 °C

36.2 bar 20.3 bar

Pressure 36.5 bar 34.5 bar
7.9 – 208 bar 52 bar

WHSV 1 – 3 h-1 N/A

LHSV 1.5 – 8 N/A
Conversion 100 % N/A
Reactor type Fixed bed Fixed bed

Table 4. Catalysts available for olefin hydrogenation Figure 7. Examples of hydrotreating reactions [9]

For references of the values in Table 4, please refer to the thesis report 13
 Selected process route

MeOH Jet fuel

Mobil MTO process MOGD process Olefin hydrogenation
ZSM-5 catalyst HZSM-5 catalyst Co-Mo/Al2O3 catalyst

14
 Aspen Plus simulation
Olefin synthesis step

Design basis: 5 ktonne/day of green methanol

Reactor conditions [4]: 2 bar, 450 C, Fluidized bed

Figure 8. Aspen Plus simulation of Mobil MTO process

15
Aspen Plus simulation
Olefin synthesis step

Mass composition of reactor oulet Mass composition of reactor oulet

stream available in literature stream in Aspen Plus model (Stream 5)

44% 43.2%

56% 56.8%

Water Hydrocarbons Water Hydrocarbons

Figure 9. Comparison of MTO reactor outlet stream with data available in literature

16
 Aspen Plus simulation
Olefin synthesis step

Hydrocarbon composition (wt%) of reactor Hydrocarbon composition (wt%) of reactor

outlet stream available in literature outlet stream in Aspen Plus model (Stream 5)

1.6%
1.4%
0.5%
0.3% 2.7%
2.3% 3.8%
35.7% 3.9% 37.0% 1.4%
5.0%

32.3%
31.8%

19.6% 20.7%

Methane Ethane Propane Butane Methane Ethane Propane Butane

Ethene Propene Butene Gasoline (C5 - C11) Ethene Propene Butene Gasoline (C5 - C11)

Figure 10. Comparison of MTO reactor outlet stream with data available in literature

17
 Aspen Plus simulation
Olefin oligomerization step

Reactor conditions [10]: 40 atm, 200 C, Fixed bed

Figure 11. Aspen Plus simulation of MOGD process

18
Aspen Plus simulation
Olefin oligomerization step

Mass composition of reactor outlet Mass composition of reactor outlet stream

stream available in literature (Stream 32) excluding non-olefinic com-
ponents
1%
2% 15% 4.5%
1.5%

25.7%

68.3%

82%

C1 - C3 C4 C5 - C9 C10+ C1 - C3 C4 C5 - C9 C10+

Figure 12. Comparison of MOGD reactor outlet stream with data available in literature

19
Aspen Plus simulation
Olefin oligomerization step

Mass composition of Stream 32

7.2% 11.2%

21.5%

60.1%

LPG Gasoline Kerosene Diesel

Figure 13. Mass composition of MOGD reactor outlet stream in terms of different final products

20
 Aspen Plus simulation
Olefin hydrogenation step

Required quantity of hydrogen: 17.1 tonne/day

Reactor conditions [10]: 36.5 bar, 350 C, Fixed bed

Figure 14. Aspen Plus simulation of olefin hydrogenation process

21
Aspen Plus simulation
Olefin hydrogenation step

Jet fuel composition (mol%) Jet fuel composition (wt%)

0.1% 0.1%
8.1% 6.7% 11.4%
5.4% 4.8%
2.2%
7.1% 21.9%
1.0%

27.5% 2.7%
1.1%

3.7%
2.6%

4.2%
42.2%
2.6%
44.6%

C8 C9 C10 C11 C12 C13 C14 C15 C16 C18 C8 C9 C10 C11 C12 C13 C14 C15 C16 C18

Figure 15. Composition of produced jet fuel on mol and mass basis

22
Aspen Plus simulation
Physical properties of produced jet fuel

Aspen Plus results for produced jet

Physical property ASTM D7566 requirement [11]
fuel

775 – 840 kg/m3 for

conventional fuel
Density @ 15 °C 741.1 kg/m3
730 – 770 kg/m3 for jet fuel
blending component

Freezing point -38.8 °C < - 40 °C

Flash point 46.3 °C > 38 °C
Viscosity @ -20 °C 3.5 mm2/s < 8 mm2/s
Viscosity @ -40 °C 5.7 mm2/s < 12 mm2/s
Gross Heating Value: 43.4 MJ/kg
Heat of combustion > 42.8 MJ/kg
Net Heating Value: 40 MJ/kg
Distillation, 10% recovered 164.9 °C < 205 °C
Distillation, final boiling point 293 °C < 300 °C
Aromatics (vol%) 0% 8 – 25%
Table 5. Comparison of jet fuel properties with ASTM D7566 requirement
23
Aspen Plus simulation
Input and output flows

Output flows (tonne/day)

Input flows (tonne/day)
2
17 231
12 443
872
30
35

2853 1253

149

881
4999

Methane Ethene Ethane

LPG Gasoline Jet fuel
Green methanol Air Green hydrogen
Diesel CO2-rich stream from catalyst regenerator Water
Purge & Off-streams

24
Aspen Plus simulation
Carbon efficiency

Carbon efficiency

3% 1%
7% 1% 10%
1%

21%

57%

Methane Ethene Ethane LPG Gasoline Jet fuel Diesel Others

25
 Heat integration
Hot utility requirement

Hot Utility Requirement (MW) before Hot Utility Requirement (MW) after
heat integration heat integration
10 0,8 10
0,8

26,1
11,1

132,1 79,5

Fired heat HP Steam MP Steam LP Steam Fired heat HP Steam MP Steam LP Steam

Figure 16. Hot utility requirement before heat integration (Total: 169 MW) Figure 17. Hot utility requirement after heat integration (Total: 101.4 MW)

26
 Heat integration
Cold utility requirement

Cold Utility Requirement (MW) before Cold Utility Requirement (MW) after heat
heat integration integration
8,2 5,9 8,2 5,9
23,4 21,6

93,5

153,6
106,6

106,6

3,4 3,4
0,4 21,9
0,4
27,5

Air Cooling water Refrigerant @ -25 C Refrigerant @ -65 C Air Cooling water Refrigerant @ -25 C Refrigerant @ -65 C
Refrigerant @ -103 C HP Steam generation MP steam generation LP Steam generation Refrigerant @ -103 C HP Steam generation MP steam generation LP Steam generation

Figure 18. Cold utility requirement before heat integration (Total: 329 MW) Figure 19. Cold utility requirement after heat integration (Total: 261.5 MW)

27
Economic evaluation
Total purchase costs of equipment

Total purchase costs = 69 M$

0.9%

4.0% 19.2%
0.8%

0.5%
35.7%

25.9%

0.1%
12.9%

Reactors Compressors Pumps

Distillation Columns Fired Heaters Double-pipe heat exchangers
Shell-and-Tube heat exchangers Vessels Catalysts

Figure 20. Total purchase costs of equipment

28
 Economic evaluation
Total capital investment

Process plant capacity: 5 ktonne/day of green methanol

Total capital investment: 715 M$

CISBL (M$) 𝐶𝐼𝑆𝐵𝐿 = 𝑓𝐿𝑎𝑛𝑔 𝑓𝑇 𝑓𝐿 ෍ 𝐶𝑃 409

COSBL (M$) 𝐶𝑂𝑆𝐵𝐿 = 0.4𝐶𝐼𝑆𝐵𝐿 163

CTDC (M$) 𝐶𝑇𝐷𝐶 = 𝐶𝐼𝑆𝐵𝐿 + 𝐶𝑂𝑆𝐵𝐿 572

CStartup (M$) 𝐶𝑆𝑡𝑎𝑟𝑡𝑢𝑝 = 0.1𝐶𝑇𝐷𝐶 57

CWC (M$) 𝐶𝑊𝐶 = 0.15𝐶𝑇𝐷𝐶 86

CTCI (M$) 𝐶𝑇𝐶𝐼 = 𝐶𝑇𝐷𝐶 + 𝐶𝑆𝑡𝑎𝑟𝑡𝑢𝑝 + 𝐶𝑊𝐶 715

29
 Economic evaluation
Raw material costs

Total raw material costs = 2.4 B$/yr

1.2%

Raw material cost

($/tonne)

Green methanol 1400

Green hydrogen 5000

98.8%

Green methanol Green hydrogen

Figure 21. Raw material costs

30
Economic evaluation
Total production costs

Total production costs = 2.6 B$/yr

3.3%

5.1%
0.5%

91.1%

Raw material costs Total variable costs (OPEX) excl. feedstock

Total fixed costs & overhead Total general expenses

Figure 22. Total production costs

31
 Economic evaluation
Total sales

Sales price
($/tonne) Total sales = 616.5 M$/yr

Methane 407 0.8%

9.2%
10.3%
2.1%
Ethane 389
0.2%

Ethene 1266

LPG 830

33.1%
44.3%
Gasoline 1382

Jet fuel 654

Diesel 1143
Methane Ethene Ethane LPG Gasoline Jet fuel Diesel

Figure 23. Total sales

32
 Economic evaluation
Breakeven price

2500

2000

1500

Current price Breakeven price 1000

($/tonne) ($/tonne)

Profitability (M$/yr)
500

Green 0
1400 214.5 0 1 2 3 4 5 6 7 8 9
methanol
-500

Jet fuel 654 5384.8 -1000

-1500

Table 6. Current and breakeven prices of green methanol and jet fuel -2000

-2500

Cost multiplication factor

Figure 24. Results of sensitivity analysis

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Conclusion

34
Recommendation

35
Questions?

36
 References

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 References

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