Sunlight to Convert CO 2 to Transportation Fuels

1. Sunlight to Convert CO2to Transportation Fuels Adviser: TalidSinno Project Author: Matthew Targett Kate McCarty Luisa Valle Elizabeth Glover Scott Danielsen

2. Purpose • To analyze the technological and economic feasibility of a facilityusing 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 2014 1 • 1.4MM bbl/d in 2015 1 • Current crude oil production through drilling • High energy expense • Releases CO2 into atmosphere 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 2014 2 • 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 2014 2 • Possibility for solar chemical processes 1 US Energy Information Administration. http://www.eia.gov/kids/energy.cfm?page=solar_home-basics 2 Solar Energy Industries Association. http://www.seia.org/research-resources/solar-industry-data

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. CR5 Overview • Adapted from: MIT Technology Review, 2010

7. CR5 Basics • Rings: • Diameter: 36 in. • Ring thickness: ¼ in. • 0.75 RPM • Fins: • Thickness: 0.5-1 mm • Height: 25.4 mm • Number of rings: 102 • Parabolic dish area: 88m2 / CR5 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 CO2Pipeline The Greengrok, Building an 'Underground Highway' for Carbon Dioxide. Duke's School of the Environment, Oct 2008.

12. Plant Layout CR5 Product Storage Tanks Water Gas Shift Section Fischer-Tropsch Section • FT Fuel Product Storage Tanks = CR5

13. Process Overview H2O H2O H2O CO CR5 Water-Gas Shift CO + H2O  CO2 + H2 H2 CO2 • Reduction • Fe3O4 • 3FeO + ½ O2 O2 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: Auxiliary

15. CR5 Overview • CO2, CO • Oxidation: • 3FeO + CO2  Fe3O4 + CO • 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

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

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

20. Water-Gas Shift • Catalyst: • 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 0.375 of the reactor • Assumed 1 second residence time • Process Conditions: • T=300°C, P=10 Bar

21. Process Flow Diagram – FT CO H2 P = 10 bar P = 20 bar Fischer-Tropsch: nCO+ (2n+1)H2 CnH2n+2 + nH2O H2O H2, CO T = 150 °C P = 20 bar 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 ofhydrocarbonscontaining n carbons • α: chain growth probability

23. Fischer-Tropsch • Catalyst: • 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% • 150-250 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 0.375 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

26. Energy Requirements • Cooling Water: • Utilized in WGS & FT Heat Exchangers, FT Reactor • Electricity: 1300-1500 MW Required

27. Power Recovery • Recovery of Heat from O2Product • 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 • 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

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

32. Capital Cost

33. Annual Operating Cost (at 95% capacity)

34. Annual Revenue (at 95% capacity)

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 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. Net Present Value

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

42. Acknowledgments We would like to thank: • Dr. Matthew Targett • Prof. TalidSinno • 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 CO2to Transportation Fuels Adviser: TalidSinno Project Author: Matthew Targett Kate McCarty Luisa Valle Elizabeth Glover Scott Danielsen

44. Financial Appendix: CR5 Cost

45. Financial Appendix: WGS and FT Reactors Water-Gas Shift Catalyst: Reactor Cost: 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 • Weight: • t­S: shell thickness • 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: FL: tube length correction FP: pressure factor based on the shell-side pressure • CB, for the floating head heat exchanger is: A: tube outside surface area.

50. Financial Appendix: Compressor • The f.o.b. pricing for the compressor is given by: • base cost, CB, for a centrifugal compressor is: PC: horsepower consumption • FD = 1.15 (process has an electric motor) • FM = Material Factor