INDIAN INSTITUTE OF TECHNOLOGY, DELHI

Under the supervision of

Prof. Sreedevi Upadhyayula

CLL794: PETROLEUM REFINERY ENGINEERING

CO₂ conversion to Jet Fuel(100 kg/hr per day jet fuel)

By
Vaishali Singh (2020CH70202)
Shasmeen Shora (2023VST9009)

ABSTRACT

The need to address climate change and establish sustainable energy sources has propelled the
advancement of eco-friendly fuel production. Particularly in the aviation sector, challenges associated
with adopting electrification for long-haul flights underscore the vital role of sustainable aviation fuel
(SAF) in effectively mitigating greenhouse gas emissions. With the persistent demand for extended air
travel, the successful integration of SAF becomes a key solution for reducing carbon footprints and
advancing environmental sustainability in the aviation industry. Simultaneously, the high-temperature
Fischer-Tropsch (HTFT) synthesis process, an innovative non-methanol mediated CO₂ hydrogenation
approach, transforms conventional methods by directly incorporating CO₂ and H₂ feedstocks within
the Fischer-Tropsch (FT) reactor. This paper enhances the comprehension of the HTFT process
through a thorough analysis of energy balance, elucidating how energy is distributed across each stage
of the process. Leveraging captured CO₂ and hydrogen, this synthesis method emerges as a
sustainable and environmentally conscious approach for synthetic kerosene production. In a world
seeking alternatives to traditional fuel sources, the HTFT process distinguishes itself as an innovative
and promising contributor to ongoing endeavours in sustainable fuel production.
1. INTRODUCTION

The Fischer-Tropsch synthesis (FTS) process, a well-established method for hydrocarbon synthesis
from a carbon source through CO hydrogenation, has taken a revolutionary turn with the advent of
high-temperature Fischer-Tropsch (HTFT) synthesis. What sets this approach apart is its departure
from the conventional reliance on a separate reverse water-gas shift (rWGS) reactor. Instead, it
introduces a groundbreaking method known as non-methanol mediated CO₂ hydrogenation.

In this innovative HTFT process, CO₂ and H₂ feedstocks are directly integrated within the
Fischer-Tropsch (FT) reactor, presenting a paradigm shift in hydrocarbon production. This deviation
from traditional methods is made possible by the use of Fe-based catalysts, which play a pivotal role
in facilitating key reactions involving CO₂ and H₂. The outcome is a synthesis of CO, H₂O, and a
range of hydrocarbons, highlighting the versatility of this approach.

For the HTFT process to achieve optimal results, it demands precise control over various reaction
conditions. Operating at high temperatures, typically around 300°C, and elevated pressures, often set
at 25 bar, is fundamental. Additionally, an excess of H₂, coupled with a catalyst effective in
suppressing CH₄ production, contributes to the process's efficiency. These controlled parameters are
essential not only for achieving satisfactory CO₂ conversions but also for optimizing the selectivity of
hydrocarbon products.

The success of this HTFT process is visualized through a meticulously designed process flow. After
the FT reactor produces the hydrocarbon mixture, adsorption units come into play to remove CO₂ and
H₂. The subsequent separation of water from the mixture is carried out through a decanting process.
The hydrotreater then transforms olefins into paraffins, further enhancing the quality of the end
product. The final stage involves processing the product stream in a distillation column, resulting in
the extraction of jet fuel at the bottom and water at the top.

This non-methanol mediated CO₂ hydrogenation process represents a promising avenue in sustainable
fuel production. By utilizing captured CO₂ and hydrogen, it not only showcases environmental
consciousness but also positions itself as an innovative pathway for synthetic kerosene production.
The efficient management of reaction conditions, coupled with the strategic process flow, underscores
the potential of this approach as a viable and environmentally friendly solution in the ever-evolving
landscape of fuel synthesis.

2. REACTIONS INVOLVED

The reactor operates at 300°C and 25 bar, where three distinct reactions occur:

Reverse Water Gas Shift Reaction: CO₂ + H₂ ⟺ CO + H₂O

Fischer-Tropsch Synthesis: nCO + (2n + 1)H₂ ⟺ CnH2n+2 + nH₂O
Side Reaction: nCO + 2nH₂ ⟺ CnH2n + nH₂O

The hydrocracker undergoes a reaction at 300°C and 30 bar. The reaction is:

Reaction: CnH2n + 2H₂ → CnH2n+2

3. PROCESS FLOW DIAGRAM

Figure: Process Flow Diagram for direct conversion of CO₂ to Jet Fuel

Figure: Symbols

4. MATERIAL BALANCE

4.1 Reactor

4.1.1 FischerTropsch Synthesis

Assuming the jet fuel to be JET-PROPULSION FUEL 5 with a molar mass of 185 kg/mol. Our goal is
to attain a jet fuel flow rate of 100 kg/hr per day.

FischerTropsch Synthesis:
nCO + (2n + 1)H₂ ⟺ CnH2n+2 + nH₂O

Thus,

Mass of Jet Fuel = [12n + 2(2n + 2)] = 185

⇒ 16n + 4 = 185
⇒ n ≈ 11

FischerTropsch Reaction: 11CO + 23H₂ ⟺ C₁₁H₂₄ + 11H₂O

Moles of Jet Fuel = (mass) / (molar mass) = 100 / 180 = 0.54 moles

By stoichiometry,

● Moles of CO = 11 x 0.54 = 5.95 moles

Mass flowrate of CO = 5.95 x 28 = 166.6 kg/hr
● Moles of H₂ = 23 x 0.54 = 12.43 moles
 Mass flowrate of H₂ = 12.43 x 2 = 24.86 kg/hr
● Moles of H₂O = 11 x 0.54 = 5.95 moles
Mass flowrate of H₂O = 5.95 x 18 = 107.1 kg/hr

4.1.2 Reverse Water Gas Shift Reaction

Reverse Water Gas Shift Reaction: CO₂ + H₂ ⟺ CO + H₂O

Assuming, equal CO Consumption in FT and Side Reaction

Now analysing Reverse Water Gas Shift Reaction: CO₂ + H₂ ⟺ CO + H₂O

Fractional Conversion of CO₂ = 0.417

● Moles of CO = 9.32 = 11.9 moles

Mass flowrate of CO in rWGS = 11.9 x 28 = 260.96 kg/hr

By stoichiometry,

● Moles of CO₂ converted in rWGS reaction = CO formed in the rWGS Reaction

⇒ 9.32 = 0.417 x (CO₂ inlet)
● Moles of CO₂ = 22.35 moles
Mass flowrate of CO₂ = 22.35 x 44 = 983.6 kg/hr
● Moles of H₂ = 9.32 moles
Mass flowrate of H₂ = 9.32 x 2 = 18.64 kg/hr
● Moles of H₂O = 9.32 moles
Mass flowrate of H₂O = 9.32 x 18 = 167.76 kg/hr

4.1.3 Side Reaction:

● Moles of CO = 3.37 moles

Mass flowrate of CO = 3.37 x 28 = 94.36 kg/hr
● Moles of H₂ = 6.74 moles
Mass flowrate of H₂ = 6.74 x 2 = 13.48 kg/hr
● Moles of H₂O = 3.37 moles
Mass flowrate of H₂O = 3.37 x 18 = 60.66 kg/hr
● Moles of C₁₁H₂₂ = 0.31 moles
Mass flowrate of C₁₁H₂₂ = 0.31 x 176 = 54.56 kg/hr

Total Mass In = CO₂ + total H₂

= 983.6 + (18.64 + 13.48 + 24.86) = 1040.58 kg/hr

Total Mass Out = C₁₁H₂₄ + total H₂O + unreacted CO₂ in recycle stream + C₁₁H₂₂
= 100 + (167.76 + 107.1 + 60.66) + 549.88 + 54.56 = 1039.96 kg/hr

Figure: Material Balance for reactor

The material balance in the reactor is:

Moles Mass flowrate (kg/hr)

CO₂ 28.54 983.6
Reverse Water Reactants
H₂ 9.32 18.64
Gas Shift
Reaction CO 9.32 260.96
Products
H₂O 9.32 167.76

CO 5.95 166.6
Fischer Tropsch Reactants H₂ 12.43 24.86
Synthesis
Reaction C₁₁H₂₄ 0.54 100
Products
H₂O 5.95 107.1

CO 3.37 94.36
Reactants
H₂ 6.74 13.48
Side Reaction
C₁₁H₂₂ 0.31 54.56
Products
H₂O 3.37 60.66

Total Mass In 1040.58 kg/hr

Total Mass Out 1039.96 kg/hr

Table: Material Balance for reactor

4.2 Flash 1

Temperature = 30°C
Pressure = 25 bar
Total Mass In = 490.08 kg/hr
Total Mass Out = 489.08 kg/hr

Streams:

C₁₁H₂₄ = 100 kg/hr

C₁₁H₂₂ = 54.56 kg/hr
H₂O = 335.52 kg/hr

Figure: Material Balance

for flash column
4.3 Hydrocracker

Reaction: C₁₁H₂₂ + H₂ ⟺ C₁₁H₂₄

Fractional Conversion of C₁₁H₂₂ = 0.9

● Mass flowrate of C₁₁H₂₂ = 54.56 kg/hr

Moles of C₁₁H₂₂ = 0.31 moles
● Moles of H₂ = 0.31 x 0.9 = 0.279 moles
Mass flowrate of H₂ = 0.279 x 2 = 0.558 kg/hr
● Moles of C₁₁H₂₄ = 0.279 moles
Mass flowrate of C₁₁H₂₄ = 50.22 kg/hr

Total Mass In = C₁₁H₂₂ + H₂

= 54.56 + 0.558 = 55.118 kg/hr

Total Mass Out = C₁₁H₂₄ + unreacted C₁₁H₂₂ in recycle stream

= 50.22 + 4.789 = 55.009 kg/hr

Figure: Material Balance for hydrocracker

The final material balance in the hydrocracker is:

Moles Mass flowrate (kg/hr)

C₁₁H₂₂ 0.31 54.56
Reactants
Hydrocracker H₂ 0.279 0.558
Products C₁₁H₂₄ 0.279 50.22

Total Mass In 55.118 kg/hr

Total Mass Out 55.009 kg/hr

Table: Material Balance for hydrocracker

4.4 Distillation Column:

Distillation Column Number of stages Stage Number of Feed Stream Boilup Ratio Reflux Ratio
1 10 5 1.16 0.5

Table: Distillation Column Specifications

5. ENERGY BALANCE

Energy balance is highly relevant in various industrial processes, especially in systems involving
components like compressors and heat exchangers. Understanding and maintaining an energy balance
is crucial for optimizing efficiency, minimizing waste, and ensuring the overall performance of these
systems.
Relevance of Energy Balance:
● Efficiency Optimization: Energy balance allows engineers to assess how effectively a system
is converting and utilizing energy. By identifying areas of energy loss or inefficiency,
improvements can be made to enhance overall system efficiency.
● Resource Utilization: In industries, where energy costs and environmental impact are
significant considerations, maintaining a proper energy balance helps in optimizing the use of
resources. This is crucial for sustainable and cost-effective operations.
● Equipment Sizing and Design: For components like compressors and heat exchangers,
understanding the energy balance is fundamental in sizing and designing equipment. It
ensures that the equipment is appropriately selected to meet the energy demands of the
process.
● Troubleshooting: Energy balance provides insights into the performance of individual
components within a system. If there are deviations from expected energy balances, it can be
an indicator of malfunctions or inefficiencies that need attention.
We can conduct a comprehensive energy balance analysis, ensuring that the energy going into a
system is accounted for and effectively utilized in various industrial processes.

The electrolyser consumption is roughly calculated based on the assumption of a specific energy
consumption of 53.79 kWh/kgH₂

Figure: Energy Balance

Energy Balance (MW)

Pin 2.18
Ein,H₂ 21.77
Ein,CO₂ 0.54
Ein,Q 1.09

Eout,Q 3.9
Ejetfuel 17.95
EC₁₁H₂₂ 0.63

Table: Energy Analysis Data

 1. COMPRESSOR (COM-1):

H1 + W1 = H2
⇒ Ein,H2 + Ein,CO₂ + W1 = mH2*hH2 + mCO₂*hCO₂
⇒ 25.06 + 0.54 + W1 = 18.64*14.63 + 983.6*1.014
⇒ W1 = 1244.47 J/s (work done by the compressor on H2 and CO₂ gas)

2. COMPRESSOR (COM-2):

W2 = H3
W2 = munreacted,CO₂*hunreacted,CO₂
⇒ W2 = 549.88*1.014
⇒ W2 = 557.57 J/s (work done by the compressor on CO₂ gas)

3. HEAT EXCHANGER (HE-1):

Q1 = mhCp,h(Ti − To)
⇒ Q1 = 335.52*4.2*(300-30) + 154.56*0.095*(300-30)
⇒ Q1 = 384.444 kJ/s

4. COMPRESSOR (COM-3):

H4 + W3 = H5
Ejetfuel + EC11H22 + W = mC11H22*hC11H22 + mjetfuel*hjetfuel
⇒ 14.15 + 4.28 + W = 54.56*0.097+ 100*0.093
⇒ W3 = -3.838 J/s (work done by the compressor on C₁₁H₂₂ and Jet Fuel)

5. COMPRESSOR (COM-4):

W4 = H6
W4 = mH₂*hH₂
⇒ W4 = 0.558*14.63
⇒ W4 = 8.164 J/s (work done by the compressor on H2 gas)

6. HEAT EXCHANGER (HE-2):

Q2 = mhCp,h(Ti − To)
⇒ Q2 = 54.56*0.097*(30-300) + 100*0.093*(30-300)
⇒ Q2 = -3939.93 J/s

COM-1 W1 = 1244.47 J/s HE-1 Q1 = 384.444 kJ/s

COM-2 W2 = 557.57 J/s HE-2 Q2 = -3939.93 J/s
COM-3 W = -3.838 J/s
COM-4 W4 = 8.164 J/s

Table: Energy Balance

6. FINANCIAL ANALYSIS SUMMARY: CAPEX and OPEX

To evaluate the economic feasibility of the high temperature FT process for converting CO₂ to jet
fuel, we will conduct a thorough examination of both Capital Expenditure (CAPEX) and Operational
Expenditure (OPEX). CAPEX encompasses the initial setup costs, including reactor design, catalyst
procurement, and system [Link],we would mainly focus on initial setup cost and reactor
design. Meanwhile, OPEX includes ongoing expenses such as utilities, maintenance, and labor. As we
delve into each equipment component outlined in the process flow diagram, we will present a detailed
breakdown of the associated CAPEX and OPEX. This analysis is crucial for gaining insights into the
financial commitments needed for the successful implementation and sustained operation of the CO₂
conversion process.

For CAPEX calculations, Appendix E of JM Douglas,Conceptual Design of chemical processes has

been consulted to obtain correlations for calculation of installation costs and the required correction
factors.
For OPEX calculations, we have used cost values (in $/KW hr) for various equipment and multiplied
it by their corresponding energy duties.

1. COMPRESSOR (COM-1):

CAPEX:
Correlation for the calculation of compressor installation cost,

Installation Cost, $ = (M&S/280)(517.5)(bhp)^0.82 Fc

Fc= 1.00 (Centrifugal motion)

M&S = 2171.6 (for year 2023)

Hp = Qin Pin / eff.

Here, eff. = 0.29 (diatomic gas)

Pin = 10.75 bar = (10.75 x144 lbf/ft² ) = 1548 lbf/ft²

Pout= 78 bar

T = Tin = 25°C = 298 K

Assuming hydrogen as an ideal gas,
PV =nRT
(dividing by t on b/s)
Pin Qin = mRT/Mt

Here, Molecular weight of hydrogen = 2 g/mol

On substituting the values and putting mass flowrate as 1040 kg/hr, we get

Qin = 0.0705 m3/hr = 1.99 x 10-3ft3 /min

Hp= 1.28 x 10-6
Compressor efficiency = 0.72
bhp= 1.78 x 10-6
Hence,
Installation Cost = $ 6723.67

OPEX:
Compressor duty = 12.97 KW
Duty cost = 0.04 $/hr
Cost = 12.97 KW × 0.04 $/hr × (300 × 24) hr/yr

Operating Cost =3735.36 $/yr

2. COMPRESSOR (COM-2)

CAPEX:
Here, T= 300°C = 573K
Also mass flow rate of CO₂ through the COM-1 is 549.88 kg/hr
Pin = 25 bar = 3600 lbf/ft²

Molecular mass of CO₂ = 44 g/mol

Pin Qin = mRT/Mt

Qin= 0.0238 m3/hr = 6.74 x 10-4 ft3/min
Hp= 1.8 x 10-7
Compressor efficiency =0.72
bhp= 2.59 x 10-7

Thus,
Installation Cost = $ 13,840

OPEX :
Compressor duty = 0.3 KW
Duty cost = 0.04 $/hr
Cost = 0.3 KW × 0.04 $/hr × (300 × 24) hr/yr

Operating Cost = 86.4 $/yr

3. COMPRESSOR (COM-3)

CAPEX:
T= 30°C = 303K
Pin= 25 bar = 3600 lbf/ft²
Molecular mass = 310 g/mol

On substituting and putting flow rate as 156.56 kg/hr

Pin Qin = mRT/Mt
We get,
Qin = 5.088 x 10-4 m3/hr = 1.44 x 10-4 ft3 /min
Hp= 4.02 x 10-9
bhp = 5.9 x 10-9
Now,
Installation Cost=$ 27,185

OPEX:
Compressor duty =0.25 KW
Duty cost = 0.04 $/hr
Cost = 0.25 KW × 0.04 $/hr × (300 × 24) hr/yr

Operating Cost = $212/yr

4. DISTILLATION COLUMN

CAPEX:
Here,
No. of Stages = 10
Boil up ratio = 1.16
Reflux Ratio = 0.5
Using the correlation for distillation column from App. E of JM Douglas
Installation cost = ((M\&S)/280) × 4.7 × D1.55 × H × Fc (⇒M&S = 2171.6)
Here, Fc = Ft + Fm+ Fs = 4.5

Ft = for packings = 1.8 (Bubble Cap)

Fm= 1.7 (SS-Stainless steel, since the alcohol used is bit acidic and may be corrosive in nature)
Fs = 1 (2 feet spacing)
N = No of plates = 6
Tower height = (N-1) × (tray spacing in feet) + (Tower bottom and top spacing margins, let them be 5
ft)
= (10-1) x 2 +5 +5
= 28 ft

Substituting in correlation,

Installation Cost = $ 21,012

OPEX:
Condenser duty = 10.9518 KW
Cost = 10.9518KW × 0.03 $/KW hr
= 2464.155 $/yr

Reboiler duty = 20.5464 KW

= 2.28$/KW hr × 20.5464
= 46.8458 $/hr
= 337289.70 $/yr

Operating Cost = Condenser Cost + Reboiler Cost = (2464.155 + 337289.70) $/yr

Operating Cost = 339,753.855 $/yr

 5. REACTOR

CAPEX:
Using the following correlation,
Installation cost = (M&S/280) 101.9 D1.066H0.082(2.18+FC)
D = diameter
H = height
Fc = FmFp
Fp = 1 ( since pressure is 1 bar)
Substituting values in the above equation, we get:

Installation Cost = $ 24,275.12

6. HEAT EXCHANGER (HE-1)

Installation Cost = ((M\&S)/280)101.3 A0.65 (2.29 + Fc)

M&S = 2171.6
U = 1000 KW/m² K
A = 1 m² = 10.7639 ft²
F=1
Fc = (Fd + Fp) Fm

Fd = 0.8 (Fixed-tube sheet)

Fp = 0.55 (P = 1000 psi)
Fm = 2.81 (CS/SS clad)

Fc = (0.8 + 0.55) × 2.81

= 3.794

On substituting the values in the given correlation, we get

Installation Cost = $ 22397.56

7. HEAT EXCHANGER (HE-2):

CAPEX:
U = 1000 KW/m² K
A = 1 m² = 10.7639 ft²
F=1

Calculations similar to the previous heat exchanger, i.e., HE-1.

Fd = 0.8 (Fixed-tube sheet)

Fp = 0.55 (P = 1000psi)
Fm = 2.81 (CS/SS clad)
Fc = (0.8 + 0.55) × 2.81
= 3.794

Installation Cost = $ 22397.56

OPEX:

Cooling water cost = 0.03 $/KW

Heat duty (as calculated in energy balance) = 64185.154 KW
Cost of utility = 0.03 $/KW × 64185.154 KW

Operating Cost = $ 1925.56

7. CONCLUSION

In conclusion, the direct conversion of carbon dioxide to jet fuel represents a promising avenue in the
pursuit of sustainable and environmentally friendly energy solutions. This innovative process,
utilising advanced technologies such as catalysis and electrochemistry, addresses the pressing issue of
CO₂ emissions by repurposing them into valuable, renewable jet fuels.
The thorough exploration of the high-temperature Fischer-Tropsch (FT) process for CO₂ conversion
has revealed promising outcomes in terms of economic feasibility and environmental impact. The
detailed calculations in cost estimation, material balance, and energy balance underscore the potential
of this process as a sustainable solution. The financial analysis, covering both Capital Expenditure
(CAPEX) and Operational Expenditure (OPEX), provides valuable insights into the investment
requirements for establishing and maintaining the high-temperature FT system.
Additionally, the material and energy balance calculations highlight the efficiency of the proposed
process. Striking a balance between resource utilisation and product yield is critical for the success of
any industrial endeavour, and the high-temperature FT process demonstrates promise in this regard.
Continuous optimization of the catalytic system, process parameters, and recycling configurations
could further enhance the efficiency and economic competitiveness of CO₂ conversion.
Its capacity to transform carbon dioxide into useful products is consistent with the global search for
environmentally and financially sustainable technology. The knowledge gathered from this research
opens up new possibilities for developments and uses in the field of carbon capture and usage.

8. ACKNOWLEDGEMENT

We want to express our sincere gratitude to Prof. Sreedevi Upadhyayula for her invaluable guidance
and unwavering support throughout this project. Her expertise, insights, and dedication significantly
contributed to the success of our work. We are truly thankful for her mentorship, which provided us
with valuable perspectives and helped shape the direction of our research. Prof. Upadhyayula's
encouragement and constructive feedback were crucial in overcoming challenges and achieving
project milestones. We appreciate her generosity in sharing knowledge and experience, which
enhanced the depth and quality of our work. This project has benefited immensely from her
mentorship, and we are grateful for the opportunity to learn under her guidance. Thank you once
again, Prof. Upadhyayula, for being an inspiring mentor and for the immeasurable impact you've had
on the successful completion of this project. Your support has been truly invaluable.
9. REFERENCES

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[Link]
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_for_Decentralized_Sustainable_Kerosene_Production
3. [Link]
4. Steam Table:
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○ [Link]
able=on
5. JM Douglas, Conceptual Design of Chemical Processes
6. M&S: [Link]
7. Yao, B., Xiao, T., Makgae, O.A. et al. Transforming carbon dioxide into jet fuel using an
organic combustion-synthesized Fe-Mn-K catalyst. Nat Commun 11, 6395 (2020).
[Link]