1. Renewable Hydrogen and Olefins by Autothermal Reforming Lanny Schmidt Department of Chemical Engineering and Materials Science University of Minnesota

4. Hydrogen and Chemicals in Millisecond Reactors Hydrogen Economy Distributed power Fuel cells Pollution abatement Renewable energy Renewable chemicals

5. Reactions CH 4  H 2 + CO  synfuels  methanol   H 2 hydrogen economy gasoline  H 2 portable power diesel  H 2 ethanol  H 2 renewable energy biodiesel  olefinsrenewable chemicals

6. Energy is the most Important Technology Issue of the 21st Century The biological revolution cannot happen without energy to drive it Extremely complex Will require radical solutions Will require replacement of fossil fuels by renewable sources The Midwest must be the source of renewables Minnesota spends over $10 billion to import energy

7. Our Ancestors Used Renewables Wood heat Beeswax and tallow light Wool, cotton, and leather clothing Horses transportation (eats oats, fertilizes the soil, and produces colts) These are completely renewable as long as they are sustainable All agricultural based products

8. The Industrial Revolution demanded a transportable liquid fuel Whale oil was the 19th Century solution whales not renewable fast enough Petroleum became the replacement gasoline, diesel, and jet fuel 10% converted into petrochemicals The energy engine of the world economy most located in bad places Saudi Arabia, Iraq, and Russia

9. Sometime We Will Switch Back to Renewables Sustainable not imported distributed no CO 2 less pollution 5 years or 50 years? What technologies? How much fossil energy? petroleum10 to 50 years natural gas20 to 100 years coal200 years The Stone Age did not end because we ran out of stones

10. Renewable Sources Wind now competitive intermittent Geothermal and hydroelectric localized Solar expensive Biomass available reliable competitive We need transportable liquid fuels ethanol biodiesel

11. Renewable Energy and Chemicals Current drivers towards Renewable Energy National Security Global Warming Rural Economic Development Renewables must compete head-to-head with fossil fuels total supply infrastructure price Subsidies critical issue not simple energy is always heavily subsidized Energy may the the most important problem in the 21st Century requires radical thinking

12. The Hydrogen Economy Code words for fuel cells 60% versus Carnot efficiency of thermal engines PEM fuel cells require hydrogen Need hydrogen wind power with electrolysis for hydrogen storage fossil fuel reforming is next generation use hydrogen for storage and transportation of energy hydrogen fueling station Distributed energy no megaplants and power lines better esthetics and safety rural areas and third world will adopt first

13. The Hydrogen Economy Nothing gained if fossil fuels are source of hydrogen reduced efficiency in reforming CO 2 global warming not helped Need renewable fuels solves all problems helps economic development use for chemicals

14. Hydrogen from Ethanol Lanny Schmidt Regents Professor Department of chemical engineering and Materials Science University of Minnesota

15. All H 2 now comes from steam reforming tube furnace Ni catalyst flames make pollutants does not scale down All olefins now come from steam cracking tube furnace homogeneous pyrolysis 1/3 of all pollution from chemical plants does not scale down Need distributed source of liquid fuels for on-board reforming

16. Steam Reformer for Hydrogen Generation Replace by system smaller than truck Enough hydrogen for house in size of coffee cup

17. Electricity from Ethanol We now have an infrastructure for ethanol  corn starch  sugar  ethanol Now supplies 10% of Minnesota’s gasoline needs Burning ethanol is inefficient use of valuable chemical Why not use it for fuel cell? 90% of energy in sugar is stored in ethanol Water in ethanol is useful to produce extra H 2

18. Renewable Hydrogen from Ethanol Produce hydrogen from a renewable fuel at short contact times for use in a fuel cell  C 2 H 5 OH  3H 2 C 2 H 5 OH + 3 H 2 O  2CO 2 + 6H 2 C 2 H 5 OH + 1/2O 2  2CO + 3H 2 C 2 H 5 OH + 2 H 2 O + 1/2O 2  2CO 2 + 5H 2

19. Why can’t it be done? Need small size for distributed power steam reforming does not scale down Ethanol very flammable Cherries Jubilee Catalytic partial oxidation endothermic no heat for autothermal reactor No one had previously reported partial oxidation

20. 0 20 40 60 80 100 200 400 600 800 1000 1200 00.511.52 Ethanol to Hydrogen Conversion X (%) Temperature o C (C/O) Ethanol Syngas UFL LFL Combustion 100% 25%

21. -20 0 20 40 60 80 100 120 0.40.60.811.21.4 S H (%) Hydrogen 25% 100% H2OH2OH2OH2O H2H2H2H2 25 100 Major Products S C (%) (C/O)

22. Stratified Catalyst Back-face Thermocouple Air HeatShields Heating Tape Insulation Automotive Fuel Injector Mixer CPOX 25 o C 140 o C 700 o C Second Catalyst: CO + H 2 O  CO 2 + H 2 First Catalyst: C 2 H 5 OH + 2 H 2 O + 1/2O 2  2CO 2 + 5H 2 400 o C WGS

23. Products Maximum Hydrogen S H (%) H 2 w/ WGS H2H2H2H2 H 2 O w/ WGS H2OH2OH2OH2O (C/O)

24. CO 2

25. photosynthesis h C 6 H 12 O 6 + 4 H 2 O 6 CO 2 +10 H 2 O ∆H o = +2540 ∆G o = +2830 sugar fuel cell 6 O 2

26. photosynthesis h 2 CO 2 + 2 C 2 H 5 OH + 4 H 2 O 6 CO 2 + 10 H 2 ∆H o = +20 ∆G o = -210 ∆H o = -140 ∆G o = -330 C 6 H 12 O 6 + 4 H 2 O 6 CO 2 +10 H 2 O ∆H o = +2540 ∆G o = +2830 sugar fuel cell 6 O 2

27. photosynthesis h 2 CO 2 + 2 C 2 H 5 OH + 4 H 2 O 6 CO 2 + 10 H 2 ∆H o = +20 ∆G o = -210 ∆H o = -140 ∆G o = -330 6 CO 2 +10 H 2 O 5 O 2 O2O2 ∆H o = -2420 ∆G o = -2290 reformed ethanol fuel cell C 6 H 12 O 6 + 4 H 2 O 6 CO 2 +10 H 2 O ∆H o = +2540 ∆G o = +2830 sugar fuel cell 6 O 2

28. What have we done? Ethanol may be a suitable renewable energy source for electricity Captures 90% of energy in carbohydrates (photosynthesis) Captures 50% of energy as electricity Very simple, small, and inexpensive reactor $5 of catalyst for 1 kW of hydrogen Work to be done improve efficiency integrate energy management and water gas shift

29. Path Forward Process commercializable use natural gas and LPG technologies Needs cheap and reliable fuel cells Hydrogen supply and demand must coincide Need to explore other renewables

30. Renewable Chemicals From Biodiesel Soy oil + CH 3 OH  biodiesel + glycerol isomers with 1, 2, and 3 double bonds 2% in Minnesota diesel pool in 2005 C-O-CH 3 O methyl linoleate 52%

31. Olefins and Olefinic Esters C-O-CH 3 O C-O-CH 3 O.. + C-O-CH 3 O C 11 = N 10

32. Renewable Chemicals biodiesel  H 2 80%  olefins90%  ethylene, propylene50%

33. Economics Ethanol available at $1.50/gallon electricity at $.06/kWh enough to supply all Minnesota electricity Biodiesel available at $2.00 gallon ($.25/lb) olefins sell for $.30/lb

34. Renewable Energy and Chemicals  sugar  ethanol  electricity CO 2 +H 2 O  biomass  carbohydrates  starch CO 2 +H 2 O  biomass  biodiesel  H 2  ethylene   -olefins  ?

35. We Must Develop Renewable Fuels No choice Transportation fuels must be liquid chemicals Biomass must be source Make high value added products Major challenge of 21st Century

36. Requires Partnerships research universities government nonprofit organizations farm organizations industries entrepreneurs

37. A $20 million initiative over 5 years for research at the University Legislative mandate funded by Xcel from CIP and RDF funds Interdisciplinary Agriculture Biology Technology Policy Clusters Hydrogen Efficiency Bioproducts and bioenergy Policy and the environment