Renewable Hydrogen and Olefins by Autothermal Reforming

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

2. Hydrogen Cluster Programs Seed Grants Micro fuel cells Bill Smyrl CEMS Hydrogen from ethanol Lanny Schmidt CEMS Biological hydrogen Mike Flickinger Biochemistry Solar hydrogen Jane Davidson ME) Photolytic hydrogen Kent Mann Chemistry Hydrogen storage Eric Gant Physics Microbial fuel cells Daniel Bond Biochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike Flickinger University Renewable Hydrogen and Chemicals from Ethanol Lanny Schmidt Mn Corn Growers Matching Grant Proposals Hydrogen Fueling Station Diesel Reforming in Autothermal Reactors Photolytic Hydrogen …

3. Renewable Energyand Chemicals Sometime we will switch to renewable chemicals and energy sustainable not imported distributed no CO2 less pollution Everyone agrees When? 5 years or 50 years? How? What sources and what technologies?

4. Renewable Energyand 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

5. 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

6. The Hydrogen Economy Nothing gained if fossil fuels are source of hydrogen reduced efficiency in reforming CO2 global warming not helped Need renewable fuels solves all problems helps economic development use for chemicals

7. Constraints Available resource Supply infrastructure Distributed Affordable Candidates ethanol $1.50/gallon soy oil $2.00/gallon

8. Renewable Hydrogen from Ethanol Lanny Schmidt Department of Chemical Engineering and Materials Science University of Minnesota

9. Catalytic Partial Oxidation Reactants • Converts hydrocarbons into valuable chemicals: syngas (H2 & CO), olefins, oxygenates, etc. • Exothermic process • Runs auto-thermally • Short contact times (Milliseconds) • Vapor phase reactions Quartz Tube Heat Shields Catalyst Products

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

11. Molecules CH4 C2H5OH C-O-CH3 O methyl linoleate 52%

12. Reactor Fuel Injector fuel air Heating Mixer Thermocouple Catalyst Insulation Products Thermocouple

13. Renewable Hydrogen from Ethanol Produce hydrogen from a renewable fuel at short contact times for use in a fuel cell C2H5OH 3H2 C2H5OH +3H2O 6H2 C2H5OH + 2 H2O + 1/2O2  2CO2 + 5H2

15. Stratified Catalyst Automotive Fuel Injector Air 25 oC Heating Tape First Catalyst: C2H5OH + 2 H2O + 1/2O2 2CO2 + 5H2 Mixer 140 oC Heat Shields CPOX 700 oC Second Catalyst: CO + H2O  CO2 + H2 Insulation WGS 400 oC Back-face Thermocouple

16. Major Products Hydrogen Maximum Hydrogen H2 w/ WGS Carbon H2 SH (%) CO2 w/ WGS CO SC (%) H2O COw/ WGS CO2 H2Ow/ WGS (C/O) (C/O)

17. CO2

18. C6H12O6 + 4 H2O 6 O2 ∆Ho= +2540 ∆Go= +2830 sugar fuel cell 6 CO2 +10 H2O photosynthesis h

19. C6H12O6 + 4 H2O ∆Ho= +20 ∆Go= -210 6 O2 ∆Ho= +2540 ∆Go= +2830 sugar fuel cell 6 CO2 +10 H2O 2 CO2 + 2 C2H5OH + 4 H2O ∆Ho= -140 ∆Go= -330 6 CO2 + 10 H2 photosynthesis h

20. 2 CO2 + 2 C2H5OH + 4 H2O C6H12O6 + 4 H2O ∆Ho= -140 ∆Ho= +20 ∆Go= -330 6 CO2 + 10 H2 ∆Go= -210 O2 6 O2 ∆Ho= +2540 5 O2 ∆Go= +2830 reformed ethanol fuel cell sugar fuel cell ∆Ho= -2420 ∆Go= -2290 6 CO2 +10 H2O 6 CO2 +10 H2O photosynthesis h

21. What have we done? Ethanol may be a suitable renewable energy source for electricity Captures 80% of energy in carbohydrates (photosynthesis) Captures 50% of energy as electricity Ready for commercialization Fuel cell is bottleneck Need to explore other renewables

22. Renewable Chemicals From Biodiesel Soy oil + CH3OH  biodiesel + glycerol CH3OOC(CH2)16CH3 methyl oleate isomers with 1, 2, and 3 double bonds 10% C16 1% in Minnesota diesel pool in 2005 C-O-CH3 O

23. Renewable Chemicals biodiesel  H2 80%  olefins 90%  ethylene, propylene 50%

24. Economics Ethanol available at $1.50/gallon electricity at $.04/kWh enough to supply all Minnesota electricity Biodiesel available at $1.70/ gallon ($.20/lb) olefins sell for $.25/lb Gasoline $1.10/gallon Biomass

25. PHOTOSYNTHETIC BACTERIAL PAINTS THAT PRODUCE HYDROGEN Michael C. Flickinger University of Minnesota BioTechnology Institute St. Paul, MN Federico Rey, Caroline Harwood University of Iowa Dept. of Microbiology Iowa City, IA

26. H2 EVOLUTION BY WILD TYPE Rhodopseudomonas palustris IN THE ABSENCE OF ATMOSPHERIC NITROGEN light ATP (Argon Atmosphere) + +N2 energized electrons (NADH, Fdred) Nitrogenase NH4+ Mutant Uptake Hydrogenase H2 Cell Material Biosynthetic precursors (CH2O) Waste Organic Compounds (source of electrons)

27. PERFUSIVE MULTI-LAYERED TRANSLUCENT LATEX COATING FOR OPTIMIZATION OF LIGHT ABSORPTION AND PHOTOTROPHIC HYDROGEN PRODUCTION(Flickinger et al., 2003,patent pending • Protective translucent coating. • Porous cell + polymer coatings. • Spacer/channel layers. • Perfusive fluid flow to cells • and gas evolution from cells. • Reflective substrate. • Total multi-layer thickness • approx. 1-2 mm.

28. CONCLUSIONS: PHOTOSYNTHETIC PAINTS MAY BE A USEFUL APPROACH • A preliminary method has been developed to make stable, translucent, acrylic/vinyl acetate latex coatings of R. palustris nitrogenase mutants on polyester under anaerobic conditions. • R. palustris coatings can produce H2 from acetate for over 400 hours in an argon atmosphere. • V-nitrogenase double mutant (∆nifH ∆anfH) has highest H2 evolution rate in latex coatings. • Coatings can be fed acetate to continuously generate H2. • Coatings are capable of frozen storage at -80˚C with retention of H2 evolution activity.

29. 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

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

31. 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

32. Hydrogen Cluster Programs Seed Grants Micro fuel cells Bill Smyrl CEMS Hydrogen from ethanol Lanny Schmidt CEMS Biological hydrogen Mike Flickinger Biochemistry (Solar hydrogen Jane Davidson ME) (Photolytic hydrogen Kent Mann Chemistry (Hydrogen storage Eric Gant Physics (Microbial fuel cells Daniel Bond Biochemistry Matching Grants Photosynthetic Bacterial Paints that Produce Hydrogen Mike Flickinger University Renewable Hydrogen and Chemicals from Ethanol Lanny Schmidt Mn Corn Growers Matching Grant Proposals Hydrogen Fueling Station Diesel Reforming in Autothermal Reactors Photolytic Hydrogen …