1. Sunlight to Convert CO2 to Transportation Fuels
Adviser: Talid Sinno
Project Author: Matthew Targett
Kate McCarty
Luisa Valle
Elizabeth Glover
Scott Danielsen

2. Purpose
To analyze the technological and economic feasibility of a facility using a proprietary reactor (CR5) to convert carbon dioxide to liquid transportation fuels using sunlight

3. State of Energy Market
2013 Global Petroleum & Other Liquids Consumption: 90.4MM bbl/d 1
Expected to grow by:
1.2MM bbl/d in
1.4MM bbl/d in
Current crude oil production through drilling
High energy expense
Releases CO2 into atmosphere
Add a petroleum consumption graph – to take away some of the wordiness of the slide
Petroleum (refined from crude oil) is the most consumed form of energy in the United States, followed by natural gas and coal
Growth is a function of higher energy requirements
1 US Energy Information Administration. Short-Term Energy Outlook (STEO), March 2014.

4. Competitive Landscape
Most solar energy is used to produce electricity in two ways:
Photovoltaic cells that change sunlight directly into electricity using solar panels arranged in arrays 1
6,000 MW expected to come online in
Concentrated solar power plants that generate electricity using concentrated solar power to heat fluid to produce steam used to power a generator 1
840 MW expected to come online in
Possibility for solar chemical processes
-over 13,000 MW cumulative solar electric capacity operating in the US- enough to power more than 2.2 million avg. american homes
-445,000 PV systems op in US today
-6,000 MW PV expected to come online in 2014
-840 MW CSP expected to come online in 2014
Most common application of solar power is to produce electricty, there are 2 ways to do this:
1. PV cells which comprise X amount of power propduction
2. solar thermal electric power plants- use concentrated solar power –only 10% of solar energy to electricity market
We also want to use concentrated solar power but instead to produce transportation fuels
There is little to no competition in our space (using solar power to produce transportation fuels)
Sources:
1 US Energy Information Administration.
2 Solar Energy Industries Association.

5. CR5: Counter-Rotating Ring Receiver Reactor Recuperator
Currently in prototype phase at Sandia National Labs
Research led by Dr. Richard Diver beginning Spring 2006
Concentrates solar energy to drive reverse redox reaction
Used in combination with Water Gas Shift and Fischer- Tropsch Reactions, creates transportation fuels

6. Adapted from: MIT Technology Review, 2010
CR5 Overview
Parabolic mirrored dish
Rings coated with Fe3O4
Top chamber = reduction Fe3O4FeO producing oxygen gas = 2300K
Bottom chamber = oxidation 3FeO + CO2Fe3O4 + CO =600K
Adapted from: MIT Technology Review, 2010

7. CR5 Basics Rings: Fins: Number of rings: 102
Diameter: 36 in.
Ring thickness: ¼ in.
0.75 RPM
Fins:
Thickness: mm
Height: 25.4 mm
Number of rings: 102
Parabolic dish area: 88m2 / CR5
Guess: Dispersed Iron Oxide on the Zirconia
Focus on fact that this is prespecified
- State where the fins are located
Kim, 2011

8. Plant Location Considerations: Solar flux Access to water
Access to CO2

9. Plant Location – Solar Flux
Southwest USA receives 7.7 kWh/m2/day at10 h/day sunlight
Adapted from: National Renewable Energy Lab (NREL), 2009

10. Plant Location – Water Access
Water industrial withdrawals in West Texas average 2.22 Mgal/day
K Averyt et al 2013 Environ. Res. Lett. 8 035046

11. Plant Location – CO2 Access
Possibility of locating the CR5 plant alongside a Power Plant & a CO2 Pipeline
The Greengrok, Building an 'Underground Highway' for Carbon Dioxide. Duke's School of the Environment, Oct 2008.

12. Plant Layout = CR5 Water Gas Shift Section Fischer-Tropsch Section
CR5 Product Storage Tanks
Water Gas
Shift
Section
Fischer-Tropsch
Section
4.3 MM barrels per year
150 CR5s
3 WGS
3FT
22 Total Storage Tanks: 3 FT oil & 19 CR5 output
Land:
Total – 77K m2 (~1/3 km on a side)
20% for roads
In CR5 field – 69% empty space for rotation of dishes
FT and WGS reactors are 15 m in diameter
FT Fuel Product Storage Tanks
= CR5

13. Process Overview H2O H2O H2O CO H2 CO2 O2 CO CO CO2 CO2 Fuels CR5
Water-Gas
Shift
CO + H2O 
CO2 + H2 H2
CO2
Reduction
Fe3O4 
3FeO + ½ O2 O2
Note that source of CO2 and H2O will be discussed later CO CO
Fischer-
Tropsch
nCO + (2n+1)H2  CnH2n+2 + nH2O
Oxidation
3FeO + CO2 
Fe3O4 + CO
CO2
CO2
Fuels

14. Process Flow Diagram Section: CR5 Section: WGS Section: FT
Section: FT
Section: Auxiliary

15. CR5 Overview CO2, CO Oxidation: 3FeO + CO2  Fe3O4 + CO Reduction:
T = 600 K
P = 0.2 atm
Reduction:
Fe3O4  3FeO + ½ O2
T = 2300 K
P = 0.2 atm
CO2
Adapted from: J. Lapp, J. H. Davidson, & W. Lipinski, “Heat Transfer Analysis of a Solid-Solid Heat Recuperation System for Solar-Driven Nonstoichiometric Redox Cycles” J. Sol. Energy Eng. 153(3), 03/22/2013.

16. CR5 Efficiency for CO production of 30% Total Throughput of 1 CR5:
199,310 kg/day
Total CO produced in 1 CR5:
95,207 kg/day of CO
CR5 Output Composition:

17. Process Flow Diagram – CR5
Highlight flow diagrams

18. Process Flow Diagram – Auxiliary
P = 10 bar
P = 0.2 bar

19. Process Flow Diagram – WGS
P = 10 bar
H2O
H2O
H2O, CO
P = 10 bar
H2O, CO
T = 300 °C
P = 10 bar CO
H2, CO
Highlight flows
H2O
H2, CO2
T = 487 °C
T = 50 °C
Water-Gas Shift:
CO + H2O  CO2 + H2
H2O

20. Water-Gas Shift Catalyst: Process Conditions:
Conventional WGS catalyst
73 wt% Fe2O3, 15 wt% Al2O3, 8 wt% Cr2O3, 4 wt% CuO
Price: $1.0 billion ($59,000 / ton)
Based on a void fraction of of the reactor
Assumed 1 second residence time
Process Conditions:
T=300°C, P=10 Bar
Expensive because of volume, maybe include price/ton of each catalyst

21. Process Flow Diagram – FT
CO H2
P = 10 bar
P = 20 bar
Fischer-Tropsch:
nCO + (2n+1)H2  CnH2n+2 + nH2O
H2, CO
T = 150 °C
P = 20 bar
H2O CO
CO, H2
CO, H2
C1-4
C5-30
T = 30 °C

22. Fischer-Tropsch Anderson-Schulz-Flory Distribution: α=0.89
Wn/n = (1 − α)2αn−1
Wn : weight fraction of hydrocarbons containing n carbons
α: chain growth probability

23. Fischer-Tropsch Catalyst: Process Conditions:
Co/Re Catalyst (Co/Re=21)
30 wt% loading Co, 4.5 wt% loading Re (65.5 wt% Al2O3)
Al2O3 support: metal dispersion 5.4%
micron diameter catalyst particles
Price: $1.3 billion ($178,000 / ton)
Largely driven by $3,000/kg Rhenium, with 4.5 wt%
Based on a void fraction of of the reactor
Assumed 1 second residence time
Process Conditions:
T=150°C, P=20 Bar

24. Fischer-Tropsch
Final Product Stream:

25. Plant Operations
Due to solar availability (avg 10 hrs/day), CR5s must operate semi-continuously
Consequently, WGS & FT reactors must operate during these same hours
Although continuous operation of these reactors is theoretically possible, storage capacity requirements are large
CR5 output storage tanks will be used to ensure steady input to the FT and WGS reactors during hours of operation
For daily shutdown: 3 product storage tanks and 19 CR5 storage tanks
For continuous FT and WGS operation: 6 product storage tanks and 128 CR5 storage tanks
Make more slides for this, and really flesh it out

26. CR5/Parabolic Dish Array
Energy Requirements
Cooling Water:
Utilized in WGS & FT Heat Exchangers, FT Reactor
Electricity: MW Required
Equipment
Electricity (MW)
WGS Compressor
541.88
FT Compressor
758.65
WGS H2O Pump
0.53
CR5/Parabolic Dish Array
0.43
1301 MW

27. Power Recovery Recovery of Heat from O2 Product
Overall Demand MW
Turbines
-79.64 MW
Combustion of Purge
Overall Electricity
303.27
Recovery of Heat from O2 Product
Combustion of Purge in FT Recycle: ~900 MW
Significant flow of H2 and light ends
Assumed Lower Heating Value & Combined Cycle

28. Power Recovery Stream at 2300K – high energy potential
O2 is run through heat exchanger creating high pressure steam, which turns a turbine

29. Plant Safety & Control Flammability & Explosions Asphyxiation
Flammable gases and liquids present in large quantities
Streams kept outside of explosion limits
Asphyxiation
CO/ CO2/ O2 monitors present throughout facility
Safety ladders to reach air safe to breath
Semi-Continous Operation
Storage Tank Control
Flows throughout plant maintained constant even with varied CR5 output due to varied solar flux
Exothermic Reactions: Temperature Controls
Recycles & Purges: Flow Controls
Trim here

30. Environmental Considerations
Reduces greenhouse gases (CO2) while utilizing a renewable energy source (solar) to create transportation fuels
End products will still produce CO2 when combusted
Large volumes of greenhouse gases (CO2, CO, H2, hydrocarbons) present throughout plant
Wastewater will have contamination from hydrocarbons and metal catalysts
Overall footprint mitigated by proximity to refineries

31. Capital Cost Price per Unit Number of Units CR5 (incl. parabolic dish)
$28 K
150
WGS Reactor
$8.3 MM/ reactor
$340 MM/catalyst 3
FT Reactor
$4.6 MM/reactor
$430 MM/catalyst
Storage Tank
$540 K 22
(3 for FT fuels, 19 for CR5 product)
Compressor
$6.1 MM
45 (19 for WGS, 26 for FT)
Pump
$47 K 15
Flash Vessel
$400 K
6 (3 for WGS, 3 for FT)
Decanter
$152 K 1
Heat Exchanger
$3.8 MM
3 (2 for WGS, 1 for FT)
Control System
$960 MM
Land
$29.8 K (total)
77,000 m2
Piping
$1.8 B (total)
5 year MACRS depreciation for all capex
Be ready to talk about why each expensive unit is so expensive and why we need so many
Purpose of this breakdown was to identify which factors are the largest drivers and have the most flexibility in terms of leading to feasibility
Piping: 68% capex (upper limit)
Control system: 36% capex

32. Capital Cost

33. Annual Operating Cost (at 95% capacity)
Carbon Dioxide ($0.035/kg)
$2.2 MM
Water ($0.001/kg)
$13.6 K
Cooling Water
$5 MM
Maintenance
(8.02% of total capital cost)
$215 MM
Startup / Shutdown
(1% of reactor capital cost)
$276 MM
Wages, Op Overhead, Admin Exp, Mgmt Incentive Comp
$93.7 MM
Electricity
$59.6 MM
CR5 module maintenance of particular importance due to the extreme heat required to break down CO2
CO2:
-cooling water? Combine with water or electricity
-be ready to address feasibility of running continuously by using storage tanks or storing in a geologic rock formation

34. Annual Revenue (at 95% capacity)
FT Fuel Sales
$900 MM
Priced at 2X crude oil (base line: $110/barrel)
Fuel Subsidy
$47 MM
38 ¢/gal for production of renewable fuels decreasing to zero in 15 yr
Carbon Credits
$224 MM
$10/metric ton for recycling waste CO2 =

35. Sensitivity Analysis Factors
Discount Rate
Economies of Scale on CR5 Price
Crude Oil Price
Fuel Subsidy
Carbon Credit
Daily Startup/Shutdown

36. Sensitivity Analysis
Best Case
Base Case
Worst Case
Discount Rate
10%
13%
18%
Price of Crude Oil
$120/barrel
$110/barrel
$90/barrel
Fuel Subsidies
$0.50/gal
$0.38/gal
$0.25/gal
Carbon credits
$15/metric ton
$10/metric ton
$0/metric ton
Economies of CR5
30%
20% 0%
Startup Cost
0.10%
1.00%
2.00%
-we couldn’t make any economic cases work and we think the reasons are: high storage costs  startup and shutdown costs, and larger facilities; CR5 vaccuum, catalyst replacement, catalyst in general
-make this slide the “dream scenario” to show how much this would help us achieve a breakeven economics
Additionally, considered the impact of operating the FT and WGS reactors continuously (no daily startup/shutdown costs, but 111 more storage units)

37. End-of-Year Cash Flow (in MM)

38. Annual After-Tax Earnings (in MM)

39. Base w/ Continuous Operation
Net Present Value
Best Case
Base Case
Worst Case
Base w/ Continuous Operation
($3.7 B)
($5.4 B)
($5.5 B)
($0.4 B)
If do not include catalysts in the capex for piping and control:
Worst: -$4.3 B
Base: -$4.2 B
Best: -$2.2 B
Continuous Base: $0.6 B

40. Other Considerations Option to sell oxygen at $56 / ton
Requires high level of compression and introduces logistical complexity in packaging and shipping to client
Separation of CO and CO2
Separation after Fischer-Tropsch requires larger reactor vessels and piping
Separation throughout the plant requires amine absorption or cryogenic distillation, with associated high capital and operating costs
Co-location with oxyfuel plant
Source of carbon dioxide and electricity
Customer for oxygen sales
Purification of carbon dioxide proves to be too costly

41. Conclusions & Recommendations
CR5 has potential to provide alternative energy source
Economic evaluation indicates economic feasibility given:
CR5 storage alternative to allow for continuous operation
Lower-cost Fischer-Tropsch catalyst
Alternative downstream process to convert CR5 output to transportation fuels
-process could be hybridized with natural gas as a co supply of CO and hydogen
-co locating with a facility that could use the O2, or near an industrial power plant to achieve addt’l rev.

42. Acknowledgments We would like to thank: Dr. Matthew Targett
Prof. Talid Sinno
Prof. Leonard Fabiano
Dr. Sean Holleran
Prof. Ray Gorte
All of the consultants that provided guidance in our weekly design meetings

43. Sunlight to Convert CO2 to Transportation Fuels
Adviser: Talid Sinno
Project Author: Matthew Targett
Kate McCarty
Luisa Valle
Elizabeth Glover
Scott Danielsen

44. Financial Appendix: CR5 Cost

45. Financial Appendix: WGS and FT Reactors
Reactor Cost:
Water-Gas Shift Catalyst:
Fischer-Tropsch Catalyst:

46. Financial Appendix: Floating Roof Storage Tanks
Tank Cost:
Maximum Capacity – 10 MM gallons (including 10% empty space)

47. Financial Appendix: Flash Vessels
Volume of the Vessel:
Relation between length and height:
Diameter of Vessel:
F.o.b. pricing for the vertical pressure vessel:
CV: purchase cost of the empty vessel
CPL: cost for platforms and ladders
FM: material factor
FM is the material factor

48. Financial Appendix: Flash Vessels
𝐶 𝑉 = exp {7.0132− ln 𝑊 ln 𝑊 }
Weight:
𝑊=𝜋 𝐷 𝑖 + 𝑡 𝑠 𝐿+0.8 𝐷 𝑖 𝑡 𝑠 𝜌
t­S : shell thickness
𝐶 𝑃𝐿 = 𝐷 𝑖 𝐿
Di : vessel inner diameter L: length of the shell

49. Financial Appendix: Heat Exchangers
The f.o.b. pricing for the heat exchanger is given by:
𝐶 𝑃 = 𝐹 𝑃 𝐹 𝑀 𝐹 𝐿 𝐶 𝐵
FL: tube length correction
FP: pressure factor based on the shell-side pressure
𝐹 𝑃 = 𝑃 𝑃
CB, for the floating head heat exchanger is:
𝐶 𝐵 = exp { − ln 𝐴 ln 𝐴 }
A: tube outside surface area.

50. Financial Appendix: Compressor
The f.o.b. pricing for the compressor is given by:
𝐶 𝑃 = 𝐹 𝐷 𝐹 𝑀 𝐶 𝐵
base cost, CB, for a centrifugal compressor is:
𝐶 𝐵 =exp { ln 𝑃 𝐶 }
PC: horsepower consumption
FD = 1.15 (process has an electric motor)
FM = Material Factor

51. Financial Appendix: Pump
Size factor, S:
𝑆=𝑄 𝐻 0.5
Q: flow rate
H: Head of the pump
Base cost, CB:
𝐶 𝐵 = exp {9.7171− ln 𝑆 ln 𝑆 }
Total Cost:
𝐶 𝑃 = 𝐹 𝑇 𝐹 𝑀 𝐶 𝐵
Electric Motor:
𝐶 𝑃 = 𝐹 𝑇 𝐶 𝐵
𝐶 𝐵 = exp { ln 𝑃 𝐶 ln 𝑃 𝐶 ln 𝑃 𝐶 − ln 𝑃 𝐶 }

52. Financial Appendix: CAPEX

53. Financial Appendix: Expenses

54. Financial Appendix: Cash Flow

55. Financial Appendix: Revenue

56. Financial Appendix: Earnings