Producing Synthetic Diesel from Natural Gas and Carbon Dioxide Using Nano-Structured Catalyst

1. Producing Synthetic Diesel from Natural Gas and Carbon Dioxide Using Nano-Structured Catalyst Dr. Chester Wilson Institute for Micromanufacturing Louisiana Tech University Carbon Capture Energy Technologies

2. Three Current Energy Challenges in Our Country: • The United States consumes 25% of the world’s oil, but produces 4%. • Oil imports are roughly half our trade deficit. A substantial part of that money funds terrorism. • Cap and Trade. The expansion of our industrial base requires energy. Traditional electricity sources produce carbon dioxide, emissions are likely to become restricted.

3. What Will Fuel Americas Transportation? • Electric cars? Current battery capacity, technology lacks. • Natural Gas cars? No manufacturing/distribution system. • Hydrogen cars? No current way to store hydrogen, or make it. Challenges are Also Opportunities! • Plenty of transportation/freight trucks on the road todayuse diesel. • What if we can make synthetic diesel from domestic energy sources like natural gas, coal and biomass? What if we could also use this to lower the carbon footprint?

4. Fischer-Tropsch Synthetic Diesel • WWI Petroleum embargo forced Germany to find a new source of diesel. 1923 Franz Fischer and Hans Tropsch discovered a way of making synthetic diesel and jet fuel from coal. 1944 124,000 barrels of diesel per day from coal.

5. Fischer-Tropsch Chemistry (a) (b) (c) CO H2O H2 catalyst catalyst catalyst • Hydrogen and carbon monoxide are heated, • pressurized, and flowed to the catalyst • (b) Hydrogen and carbon “stick” to the catalyst, • water diffuses away • (c) Hydrocarbon chains form - diesel

6. Catalyst Material Comparison • Iron, cobalt are best practical catalysts

7. Catalyst Material Comparison • Iron, cobalt are best practical catalysts • Cobalt is more expensive.

8. Catalyst Material Comparison • Iron, cobalt are best practical catalysts • Cobalt is more expensive. • But cobalt makes more diesel.

9. Catalyst Material Comparison • Iron, cobalt are best practical catalysts • Cobalt is more expensive. • But cobalt makes more diesel. • But if you foul the cobalt, no more diesel.

10. Current Nanostructured Catalyst vs. Our Nanowire Catalyst Nanotube Nanowire Fast process (minutes) Open structure does not encourage molecular stagnation Single crystal: no oxidization • Slow process (hours) • Prone to “clogging” via waxes and coking • Very difficult to refurbish

11. Hydrocarbon Distribution 94% of product is diesel; Industrial iron catalysts: 35% 18 16 14 12 10 8 6 4 2 0 C6-C10: Gasoline C10-C20: Diesel C30+: Wax Percent of Total Product 8 10 12 14 16 18 20 22 24 Hydrocarbon Number

12. Clean Coal Electricity One large source of hydrogen and carbon monoxide is clean coal gasification. But this also produces carbon dioxide.

13. Carbon Dioxide Utilization What we have found is similar nanostructured catalyst in nickel breaks down carbon dioxide and natural gas to carbon dioxide and hydrogen. Two stage reactors produce diesel where 30% of the carbon is from greenhouse gases.

14. Small Scale Reactor Economic testbed reactor being constructed at Louisiana Tech. Funded by the Department of Energy. Heater tubes Reactor tubes

15. Scales of Testing • Technology has been licensed by Carbon Capture Energy Technologies • Startup company out of Ruston • Seeking to construct a turnkey system at the Hanesville fields.

16. Thank You.Questions?

18. Solution: Nanostructuring • High surface area to volume ratio • More reactions from less catalyst • Lower fabrication cost from less material • High Crystallinity • Resistance to oxidation • Resistance to sulfur contamination

19. Fabrication: Cobalt Nanotubes • Template Wetting • (a)/(b) Cobalt salt is deposited into pores • (c) Salt and water begin evaporating • (d) Cobalt is left behind, coating pores (a) (b) (c) (d)

20. Fabrication: Cobalt Nanowires + - • Magnetically-enhanced electrodeposition • Cobalt is electrodeposited into alumina pores • Neodymium-Iron-Boron magnet constricts deposition

21. Cobalt Problems • Cobalt oxidizes through grain boundaries (crystal structure defects) • Cobalt is less resistant to sulfur contamination than iron • Cobalt costs too much for bulk manufacture Grain Boundaries

22. Microscale Reactor • Provides real-time test data of hydrocarbon distribution • Can test multiple catalysts simultaneously • Easy to manufacture (simple lithography, etching) • Inexpensive to manufacture and test • Determines what to test in the Small-Scale Reactor

23. Microreactor Design Catalyst Channels Cobalt Nanostructures Metal -on-glass lithography Alumina- on-chrome heater 1cm 5 µm

24. Heater Capacity

25. Summary • Synthetic diesel is pollution free • More sources than petroleum • Iron catalysts are not economically viable • Microreactors allow rapid testing • Cobalt is practical as electrodeposited nanowire: • Durable • Inexpensive • Higher productivity than industrial catalysts

26. Carbon Capture Synthetic FuelsIDEA PitchJohn M RolloDavid VealsAdvised by: Dr. Chester Wilson and John McDonald

27. Societal Problems: 1) US dependence on foreign oil 2) CO2 pollution How do we profit from this? Coal plants will pay us to take their waste CO2 , combine it with cheap domestic natural gas to produce and sell LOTS of diesel fuel

28. Other Alternatives: • Electric & Hydrogen vehicles • Biofuels • Direct competition • Sasol – Coal to syngas to diesel • Shell - Oxidized methane to syngas to diesel

29. Our Solution: • Create synthesis gas from CO2 and CH4 • for stock to produce diesel fuels • Dr. Chester Wilson’s IP • Nickel catalyst with plasma cleaning • Nanostructured GTL Cobalt catalyst

30. Design Specifics: Pilot System: Target of 1 L/day Breakdown reactor - Furnace in a quartz tube - Nickel Catalyst Fischer Tropsch GTL Reactor - 20 linear ft plug flow reactor - Cobalt Catalyst

31. Fischer-Tropsch Process • Carbon-containing feedstock (coal, natural gas, landfill gas, biomass) • Solid feedstocks are gasified (heating in steam) • Resulting syngas fed into reactor • Catalyst reacts the syngas to produce synthetic diesel

32. Carbon Capture: • Synthesis yields net CONSUMPTION of CO2 • Ability to utilize CO2 from nearly any source • Capture & Utilize industrial pollution • Allows industry growth

33. Economics: Our process converts 1000 f of NG (~$3.30) into about 2.6 gal of diesel (~$7.02) US Department of Energy & National Science Foundation grants are providing research & development costs Estimated DOE subsidies ~$1.60/gallon

34. Market: • 1,417 Coal-fired generators in the US • Produce ~2 lbs CO2 per kW/h • About 1.8 billion metric tons per year • Over 7 billion barrels of proven natural gas reserves in the US • Diesel consumed?

35. Conclusion: • Domestically produced fuels • Unique carbon-capturing synthesis • LA Tech IP yields efficiency improvement over existing technology • Questions?

36. Natural Gas, a Domestic Resource T. Boone Pickens is currently communicating a vision to America.Develop wind power to produce electricity, replacing natural gas generators, so the natural gas can be used to power cars. The plan is a refreshing path to American energy independence, but there are some challenges on implementation of natural gas as an auto fuel: Challenge #1: There exists little infrastructure to distribute compressed natural gas at service stations. Challenge #2: There are few mass produced natural gas powered cars. Carbon Capture Energy Technologies

37. Conversion of Natural Gas to Diesel Fischer-Tropsch conversion of syngas (molecular hydrogen and carbon monoxide) produced from woodchips, coal, or natural gas into diesel is well known, and currently commercialized to a limited extent. To become economical, most of these facilities are large. Carbon Capture Energy Technologies has developed or shared use agreements on several new technologies to reduce the size of an economic facility. We have use agreements for nanostructured catalysts that increase the surface reactivity, and a new reactor technology that allows enhanced syngas production by combining impure natural gas and carbon dioxide. This syngas is then Fischer Tropsch converted to diesel. Carbon Capture Energy Technologies

38. Current Problems with Clean Coal Technology Coal is amazingly abundant in North America, and a critical component to electricity production. Many advances in technology have minimized the environmental impact of coal generation. Sulfur and ash reduction techniques are working, acid rain is something we don’t hear about anymore. One problem not yet well addressed is carbon dioxide production, which is heavily produced in this process, and is the most common greenhouse gas. We do hear about that in the news. Carbon Capture Energy Technologies

39. Carbon Dioxide Sequestering and Carbon Credits One possible solution is carbon dioxide sequestering, pumping the carbon dioxide back into the ground. This is losing ground politically, and both political parties are advocating some form of carbon cap; a limit to the CO2 production. This would make carbon credits very expensive, but appears needed to reduce greenhouse gas emissions. As our diesel production process using natural gas consumes CO2, our company would receive revenues by integration into these coal gasification units…even before the diesel was sold. Carbon Capture Energy Technologies

40. Small Scale Wood and Waste Gasification Units The new farm bill is offering $1.01 subsidization for cellulose based fuel. Carbon Capture Energy Technologies has proprietary wood and waste gasification technology that focuses on smaller, mobile units with flexible combustion chambers that can utilize landfill waste. This landfill waste can be converted into syngas that can replace natural gas as a way to heat livestock facilities. Carbon Capture Energy Technologies

41. Corporate Officers CARBON CAPTURE ENERGY TECHNOLOGIES Dr. Sam Dauzat, President Dr. Chester Wilson, VP Technology John McDonald, VP Operations Contact Information svdauzat@latech.edu 318.257.3446 Carbon Capture Energy Technologies